IIT-JEE

ATOMIC STRUCTURE
IIT-JEE Fundamental
Particles
1) The mass of an electron is
1) 0.000549 amu 2) 1.00727amu 3) 1.00867 amu 4) None
Note : Mass of an electron = 9.1x10 -31 Kg
= 5.49 x 10-4 amu
2) The charge on an electron is
1) 9.1 x 10-31 coulombs 2) 1.602 x 10-19 coulombs
3) 4.8 x 10-10 coulombs 4) None
3) The mass of a proton is equal to
1) 1.6726 x 10-24 grams 2) 1.00727 amu
-27
3)1.6726 x 10 Kg 4) All
4) The mass of a neutron is
1) 1.6749 x 10-27Kg 2) 1.00867 amu
3) Both 1 & 2 4) None
5) The charge on a neutron is
1) + 1.6 x 10-19 coulombs 2) -1.6 x 10-19 coulombs
-10
3) 4.8 x 10 e.s.u 4) None
6) 1 amu is equal to
1) 1.6726 x 10-27 Kg 2) 1.6605 x 10-27 Kg 3) 1.6749 x 10-27 Kg 4) None
7) The symbol used to represent a - particle is
1) +1e0 2) -1e0 3) +1p1 4) 2He4
Note : - particle is nothing but an electron
8) The ratio of mass of proton to that of an electron is
1
1) 2) 1836 3) 1839 4) 1
1836
9) The ratio of mass of neutron to that of an electron is
1
1) 1839 2) 3) 2 4) 1836
1836
10) The ratio of specific charge of electron to that of a proton is
1
1) 1836 2) 3) 1839 4) None
1836
Charge e
Note : Specific charge = mass
=
m

11) The equation relating the characteristic frequency ( ) of X-rays emitted by anti-cathode and atomic
number (Z) of the metal used as anti-cathode, given by Moseley is
2
1) a( z b ) 2) a( z b ) 3) z 4) a ( zb )
12) Charge on electron was experimentally determined by
1) Millikan 2) Goldstein 3) Chadwick 4) J.J.Thomson
13) Choose the incorrect statement
1) Nucleus occupies very small fraction of atom and most of the atom is empty, hence most of the
alpha particles passed through the gold foil undeflected during - particle scattering experiment.
2) Entire mass of the atom is concentrated in the nucleus and the mass of electrons is negligible.
3) Nucleus carries positive charge due to presence of protons in it.
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4) Most of the atom is not empty and hence the -particles are deflected back.
14) The e/m value of cathode rays in a discharge tube is
1) always same irrespective of the gas taken 2) different for different gases
3) same only when noble gases are taken 4) None
15) Neutron was discovered by
1) Thomson 2) Chadwick 3) Goldstein 4) Rutherford
16) The highest value of e/m is observed for anode rays when the discharge tube is filled with
1) N2 2) H2 3) O2 4) He
17) Which of the following pair have identical values of e/m
1) A proton and a neutron 2) A proton and a deuterium nucleus
3) A deuterium nucleus and an -particle 4) An electron and -rays
18) Choose the correct increasing order of e/m values for e,p,n and - particle
1) p < n < < e 2) e < p < < n 3) n < p < e < 4) n < < p < e
19) The e/m value of electron is
1) 9.1 x 10-31 Kg 2) 1.602 x 10-19C 3) 1.759 x 1011C.Kg -1 4) Zero
13 14
20) The relation between 6C and 6C is
1) isobars 2) isotopes 3) isotones 4) None
14
21) The isobar of 6C is
1) 8O16 2) 6C13 3) 7N14 4) 2Be4
22) Isotones contain same number of
1) electrons 2) protons 3) positrons 4) Neutrons
23) The triad of nuclei that is isotonic is
1) 6C14, 7N15, 9F17 2) 6C12, 7N14, 9F19 3) 6C14, 7N14, 9F17 4) 6C14, 7N14, 9F19
24) The radius of atomic nucleus is of the order of
1) 10-10 cm 2) 10-13cm 3) 10-15cm 4) 10-8cm
35 37
25) The natural abundance of 17Cl and 17Cl is approximately 75% and 25% respectively. The molar
atomic mass of chlorine will be
1) 36 g 2) 35.5g 3) 36.5g 4) 37g
26) Which of the following reaction led to the discovery of neutrons.
1) 6 C 16 1 p1 7 N 14 0 n1 2) 4 Be9 2 He 4 6 C 12 0 n1
3) 5 B11 1 D 2 6 C 11 0 n1 4) 4 Be8 2 He 4 6 C11 0 n1

Quantum Theory
1) Quantum theory had suggested
1) Emission of energy is continuouss
2) Energy is emitted discontinuously in the form of quanta
3) Energy of the radiation is quantized.
4) Both 2 & 3
2) The wavelength of a radiation emitted by a sodium lamp is 600 nm. The frequency is
1) 5 Hz 2) 5 x 1014 Hz 3) 500 Hz 4) 5 x 1015 Hz
3) If the light radiation from neon atom has a wavelength of 300 nm, then the energy of the
photon being emitted is
1) 6.626 x 10-19 J 2) 1.1 x 10-10 J 3) 2 x 10-19 J 4) 3.3 x 10-12 J
4) Violet light is able to eject electrons from the surface of potassium metal, whereas red light cannot.It
is because,
1) the intensity of violet light is greater than that of red light.
2) the frequency of red light is lower than that of violet light and its energy is not sufficient to knock out
the electrons.
3) the wavelength of violet light is greater than that of red light
 3
4) None
5) Electrons with a kinetic energy of 6.023 x 104 J/mol are evolved from the surface of a
metal, when it is exposed to a radiation of wavelength of 300nm. The minimum amount of
energy required to remove one electron from the metal atom is
1) 5.626 x 10-19J 2) 3 x 10-19J 3) 6.02 x 10-19 4) 6.62 x 10-34J
Formula : E = W + KE
E = Energy of radiation
W = Work function
KE = Kinetic energy.
6) Electrons with kinetic energy of 3.313 x 10-24 J are evolved when a light radiation of 5 x109 s-1 of
frequency falls on a metal surface. The threshold frequency of the metal is
1) 5 Hz 2) 4.5 x 109 Hz 3) 500 Hz 4) 3 x 1024 Hz
Formula : K.E = h ( - 0)
7) When the frequency of light incident on a metalic plate is doubled, the kinetic energy of
emitted photoelectrons will be
1) Doubled 2) Halved 3) More than doubled 4) Unchanged.
Hint : h = W + KE1
2h = W + KE2
2W + 2KE1 = W + KE2
KE2 = 2KE1 + W
8) Photo electrons are ejected from metals A & B when a light beam of wavelength 1 is used to irradiate
them. But electrons are ejected only from metal B, when another radiation of wavelength 2 is used.
Then the false statement among the following is
1) Electrons need more energy to escape from metal A
2) 2 1
3) Threshold frequency of A is higher than that of metal B
4) When irradiated by light beam of wavelength 1 , the electrons ejected out from metal A have
more kinetic energy.
9) Photo-electrons are evolved when a metal is exposed to violet light. But no electrons are evolved
when yellow light is used. If the metal is exposed to red light, the photo-electrons are
1) evolved when the intensity (of red light) is increased
2) not evolved
3) evolved even at low intensities
4) evolved only when a thin sheet of metal is used
10) The value of Plancks constant is
1) 6.625 x 10-34 cal.sec 2) 1.584 x 10-34 cal.sec
3) 6.625 x 10-27J.sec 4) 6.625 x 10-34 erg.sec
Note: 1 calorie = 4.184 Joule
11) The number of photoelectrons emitted during photoelectric effect is proportional to
1) Intensity of incident beam 2) Work function
3) Frequency of incident beam 4) Velocity of incident beam

Bohrs Atomic Model

1) The angular momentum of an electron revolving in L - shell of hydrogen atom is
h h 2h 3h
1) 2) 3) 4)
2 2
2) The angular momentum of electron in Bohrs first orbit of hydrogen atom is x what will be its angular
momentum in the Bohrs first orbit of He+ ?
1) 2x 2) 4x 3) x 4) x2
3) The force of attraction between nucleus and an electron is given by
 4
2 2 2
e e Ze Ze
1) 2) 3) 4)
r r r r2
4) Bohrs equation to calculate the radius of an orbit is
n 2h2 n2h2 n 2 h 2 .4 0 n2h2
1) 2) 3) 4)
2 2 me 2 4 2 me 2 Z 2 4 2 me 2 Z 4 2 me 2 Z 4 0
5) The radius of Bohrs orbit is proportional to
n2 n
1) n 2) 3) Z 2 4)
Z Z
6) The radius of Bohrs second orbit in hydrogen atom is
1) 0.539 A0 2) 2.116 A0 3) 0.2116 A0 4) None
2+
7) The radius of Bohrs first orbit in Li is
1) 0.0587 pm 2) 17.63 pm 3) 176.3 pm 4) 0.529 pm
+ 3+
8) The ratio of radius of first orbit of He to that of Be is
1) 2 : 1 2) 1 : 2 3) 1 : 4 4) 4 : 1
9) The radius of first orbit in H-atom is equal to the radius of
1) 1st orbit in He+ 2) 2nd orbit in Li2+ 3) 2nd orbit in Be3+ 4) 2nd orbit in He+
10) The ratio of radii of first three orbits in hydrogen atom is
1) 1 : 4 : 9 2) 1 : 2 : 3 3) 1 : 2 : 4 4) 9 : 4 : 1
11) The distance between successive orbits while going away from nucleus
1) decreases 2) increases
3) first decreases and then increases 4) unchanged
12) Bohrs expression to calculate the energy of electron in a given orbit is
2 2 me 4 z 2 2 2 me 4 z 4 0
1) 2
2)
n 2 h 2 4 0 nh
2
4 2 me 4 z 2 4 0 4 2 me 4 z
3) 4)
n2h2 nh 2
13) The potential and kinetic energies of Bohrs orbits are expressed as
Ze2 1 Ze 2 Ze 2 1 Ze2
1) & 2) &
r2 2 r2 r 2 r
Ze 2 Ze2 Ze2 1 Ze 2
3) & 4) &
r r r 2 r
14) The total energy and potential energy of electron in a given orbit are expressed as
1 Ze 2 1 Ze 2 Ze2 1 Ze 2
1) & 2) &
2 r 2 r r 2 r
1 Ze 2 Ze2 1 Ze 2 Ze 2
3) & 4) &
2 r r 2 r r
15) The energy of electron in the 1st orbit of hydrogen atom is
1) -13.6 eV 2) -2.18 x 10-18J 3) -5.21 x 10-19 Calories 4) All
16) The energy of one mole of electrons present in Bohrs first orbit of hydrogen atoms is
1) - 313.6 Kcal 2) -1312 kJ 3) Both 1 & 2 4) None
17) The energy of electron in second shell of hydrogen atom is
 5
1) +3.4 eV 2) -3.4 eV 3) -13.6 eV 4) + 13.6 eV
18) The energy of electron in the ground state of He+ ion is
1) -13.6 eV 2) + 54.4 eV 3) - 27.2 eV 4) - 54.4 eV
19) The kinetic and potential energies of electron in the ground state of hydrogen atom are respectively.
1) +13.6 eV & -13.6 eV 2) + 13.6 eV & - 27.2 eV
3) -136 eV & + 13.6 eV 4) 27.2 eV & - 13.6 eV
20) The energy of an electron in the M-shell of hydrogen atom is x eV. The energy of electron in its L-shell
is
x x x x
1) eV 2) eV 3) eV 4) eV
9 4 4 9
21) The ratio of energies of electrons in first three Bohrs orbits in hydrogen atom is
1 1 1 1 1 1 1 1
1) 1: : 2) 1: : 3) : :1 4) : :1
4 9 2 3 3 2 9 4
22) The energy difference between two successive orbits while going away from the nucleus
1) decreases 2) increases 3) remains same 4) first decreases and then increases

23) The ratio of energies of electrons in the ground states of H, He+ and Li2+ is
1 1 1 1
1) 9 : 4 : 1 2) : :1 3) 1: : 4) 1 : 4 : 9
9 4 4 9
24) The energy of an electron in the first orbit of hydrogen atom is -y Joule. The kinetic energy of electron
in the second orbit will be
y y y y
1) - Joule 2) Joule 3) Joule 4) Joule
4 2 2 4
25) The potential energy of electron present in the ground state of Li2+ ion is
3e 2 3e 3e 2 3e 2
1) + 2) 4 r 3) 4)
4 0 r 0 4 0 r 4 0 r 2
26) The energy of electron in the first orbit of hydrogen atom is equal to the energy of electron in the
1) 2nd orbit of He+ 2) 3rd orbit of Li2+ 3) 4th orbit of Be3+ 4) All
-18
27) The energy of electron in the ground state of hydrogen atom is -2.18 x 10 J. The potential energy
of electron in the first excited state of He+ ion is
1) - 2.18 x 10-18 J 2) + 2.18 x 1018 J 3) -4.36 x 10-18J 4) - 1.09 x 10-18J
28) The velocity of an electron in Bohrs orbit is expressed as
2 Ze 2 2 Z 2e 4 2 me2 2 Ze
1) 2) 3) 4) 2 2
nh nh nh nh
29) Choose the incorrect statement
1) The energy of electron increases with n value of orbit
2) The kinetic energy of electron decreases with n value of orbit
3) The potential energy of electron increases with n value orbit
4) The velocity of electron increases with n value of orbit
30) The ratio of velocities of electrons in first three orbits of hydrogen atom will be
1 1 1 1
1) 1 : 4 : 9 2) 1: : 3) 1: : 4) 1 : 2 : 3
2 3 4 9
31) The velocity of electron in first orbit of hydrogen atom is
1) 2.188 x 108 cm.sec-1 2) 13.6 cm sec-1 3) 2.188 x 108m.sec-1 4) 0.529 x 10-18 cm sec-1
32) If the velocity of an electron is x cm.sec-1 in the ground state of hydrogen atom, the velocity in the
 6
second orbit is
x x x2
1) cm.sec-1 2) x2 cm.sec-1 3) cm.sec-1 4) cm.sec-1
4 2 4
33) Rydbergs constant can be expressed as
2 2 me 4 z 2 2 2 me 4 2 2 me 4 4 2 me4
1) 2) 3) 4)
ch3 n2h2 ch3 ch3
34) The value of Rydbergs constant is
1) 1.096 x 105 cm-1 2) 109677 cm 3) 109.677 m-1 4) 1.096 x 103 m-1
35) An electron jumps from 4th orbit to 2nd orbit. The spectral line corresponding to this transition will be
observed in
1) Lyman series 2) Paschen series 3) Pfund series 4) Balmer series
36) The wave number of limiting line in Lyman series of hydrogen atomic spectrum is
1) 109677 cm-1 2) 27892 cm-1 3) 13142 cm-1 4) 42314 cm-1
37) The ionisation energy of hydrogen atom is
1) 13.6 eV 2) 3.4 eV 3) 1.51 eV 4) 0.85 eV
38) The spectral line corresponding to longer wavelength in hydrogen atomic spectrum is
1) Limiting line in Pfund series 2) First line in Lyman series
3) Limiting line in Lyman series 4) First line in Pfund series
39) A spectral line is observed in the visible region of emission spectrum of hydrogen. The probable
transition corresponding to this line
1) n = 2 n = 5 2) n = 2 n = 3 3) n = 4 n = 2 4) n = 5 n = 3
40) The ratio of energies of first three lines in Lyman series is
1 1 1 3 8 15 4 9 16
1) 1 : 2 : 3 : : 2) 3) : : 4) : :
2 3 4 4 9 16 3 8 15
41) The wave number of a spectral line for a given tranistion is x cm for He+, then its value for Be3+ for
-1

same transition is
x -1
1) x cm-1 2) 4 x cm-1 3) cm 4) 16 x cm-1
4
42) The energy of electron in the infinite orbit is
1) +13.6 eV 2) 1 eV 3) 4) zero
43) A hydrogen atom is supplied with 10.2 eV of energy in its ground state. The highest energy level into
which the electron can be excited is
1) 3rd 2) 4th 3) 2nd 4) 10th
44) The energy required to remove an electron from a hydrogen atom in its 1st excited state is
1) 13.6 eV 2) 3.4 eV 3)1.51 eV 4)0.85 eV
45) The wavelength corresponding to -line in Balmer series is
1) 6564 A0 2) 3282 A0 3) 15232 A0 4) None
46) The number of spectral lines formed when an electron undergoes all possible transitions between
6th orbit and 1st orbit is
1) 6 2) 15 3) 30 4) 21

Use formula :

n n 1
; where n = n 2 n1
2
47) An electron in the ground state of hydrogen atom absorbed 12.75 eV of energy and get excited. The
number of spectral lines formed due to all possible transitions when electron jumps back from highest
possible energy level, during this excitation, to L-Shell of the atom is
1) 15 2) 3 3) 1 4) 10
 7
h
48) The difference in angular momentum of two bohrs orbits is 3 . The number of all possible elec-
2
tronic transitions between these two orbits is
1) 3 2) 12 3) 6 4) 1
49) The ratio between Kinetic energy and total energy of electron in atoms according to Bohrs model is
1) 1 : 1 2) 1 : -1 3) 1 : 2 4) -2 : 1
50) The wave number of limiting line of Paschen series of hydrogen atomic spectrum is equal to
RH R R
1) RH 2) 3) H 4) H
25 9 16
51) The lines in Lyman series of hydrogen atomic spectrum are formed in
1) Visible region 2) Far IR region 3) UV region 4) Near IR region
52) Bohrs theory could not explain
1) Zeeman effect 2) Fine atomic spectrum 3) Stark effect 4) All
Quantum Numbers
1) Match the following
A) Principal quantum number (n) 1) Neils Bohr
B) Azimuthal quantum number (l) 2) Uhlenbeck & Goudsmit
C) Magnetic quantum number (m) 3) Lande
D) Spin quantum number (s) 4) Sommerfeld
Choose the correct matching
A B C D
1) 1 2 4 3
2) 1 4 3 2
3) 1 3 2 4
4) 3 1 4 2
2) In order to explain fine hydrogen atomic spectrum, Sommerfeld proposed.
1) Principal quantum number 2) Spin quantum number
3) Azimuthal quantum number 4) Magnetic quantum number
3) Magnetic quantum number (m) is proposed by Lande, in order to explain
1) Low resolution hydrogen atomic spectrum 2) Fine hydrogen atomic spectrum
3) Zeeman effect 4) Spin - Spin coupling
4) The wrong statement about principal quantum number n is
1) It is used to identify the main energy level or shell
2) It is used to determine the size and energy of orbit
3) It is used to calculate the number of orbitals in the nth shell and is given by n2.
4) It is used to determine the orientation of orbital
5) The quantum number which is used to determine the shape of orbital is
1) Principal quantum number (n) 2) Azimuthal quantum number (l)
3) Magnetic quantum number (m) 4) Spin quantum number (ms)
6) The orbital angular momentum of electron is precisely given by
nh h h h
1) 2) l l 1 3) s s 1 4) n n 2
2 2 2 2
7) The number of subshells in a given main shell n is equal to
1) n - 1 2) n2 3) n n 1 4) n
8) The possible subsidiary quantum number values of sublevels in the 3rd shell are
1) l = 1, 2 & 3 2) l = 1 & 2 3) l = 0, l & 2 4) l = 1, 2, 3 & 4
9) Match the following
 8
Azimuthal quantum number Shape of orbital
A) l = 0 1) Dumb-bell
B) l = 1 2) Diffused
C) l = 2 3) Spherical
D) l = 3 4) Double dumb-bell
The correct matching is
A B C D
1) 3 2 1 4
2) 3 1 2 4
3) 3 1 4 2
4) 2 3 1 4
10) The n & l values of 4f orbital are
1) 4 & 3 2) 4 & 4 3) 4 & 1 4) 3 & 3
11) The number of orbitals in a given shell n is equal to
1) 2n 2) 2n2 3) n2 4) 2n - 1
12) The number of orbitals in given sub shell l is equal to
1) l + 1 2) l + 2 3) 2l + 2 4) 2l + 1
13) The number of orbitals in l = 2 subshell will be
1) 2 2) 3 3) 5 4) 1
14) The significance of magnetic quantum number (m) is
1) It denotes the size of orbital 2) It represents the shape of orbital
3) It indicate the orientation of orbital 4) It represents angular momentum of orbital
15) The possible values of magnetic quantum numbers of orbitals in a subshell l= 2 are
1) -2, -1, +1, +2 2) -2, -1, 0, +1, +2 3) -1, 0, +1 4) 0, +1, +2, +3
16) The maximum number of electrons that can be accommodated in sub shell l = 2
1) 2 2) 5 3) 4 4) 10
Note : The no.of electrons in subshell l = 4l + 2
17) The maximum number of electrons that can be accommodated in an orbital is
1) 2 2) 1 3) 4 4) 1 / 2
18) The values of spin quantum number can be
1 1 1 1
1) 2) 3) or 4) 0 or 1
2 2 2 2
19) Spin quantum number was proposed by
1) Goudsmidt & Uhlen beck 2) Lande 3) Neils Bohr 4) de Broglie
20) The number of orbitals present in the shell with n = 4 is
1) 4 2) 8 3) 16 4) 32
Note : The number of orbitals in given shell, n is given by n2
21) The maximum number of electrons that can be present in a main energy level n = 3 is
1) 3 2) 18 3) 6 4) 9
22) The quantum number that is not possible for electron in 4d orbital is
1) l = 2 2) s = + 1 / 2 3) m = 0 4) m = + 3
23) 2px and 2py orbitals differ in their
1) energy 2) shape 3) orientation 4) l value
24) The notation of orbital with n = 3 and l = 1 is
1) 3s 2) 3p 3) 3d 4) 2p
25) The incorrect set of quantum numbers for an electron will be
1) n = 3, l = 1, m = 0, s = + 1 / 2 2) n = 2, l = 0, m = 0, s = - 1 / 2
3) n = 4, l = 3, m = -3, s = - 1 / 2 4) n = 3, l = 2, m = +3, s = + 1 / 2
26) The number of p orbitals present in a shell with n = 4 is
1) 4 2) 12 3) 10 4) 3
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de Broglies wave concept

1) The wave length of an electron can be expressed as
h h h2 h
1) 2) 3) 4)
2 mv n n
2) The electron revolving around the nucleus behaves as a stationary wave only when the circumference
of its orbit is equal to
1) Fractional multiple of its wavelength. 2) Integral multiple of its wavelength.
3) Velocity of electron 4) Radius of orbit
3) Quantization of angular momentum of an electron in a stationary orbit can be justified by using.
1) Bohrs theory 2) Heisenbergs theory 3) de Broglies theory 4) Quantum theory
4) The velocity of an electron is 6.626 x 104 m.s-1. The wavelength of electron is
1) 110 A0 2) 232 A0 3) 91 A0 4) 323 A0
5) The ratio of wavelength of proton to that of electron which are moving with same velocity is
1) 1 : 9 2) 1836 : 1 3) 1 : 1836 4) 1 : 2
6) The number of waves produced by electron wave in Bohrs 3rd orbit is
1) 1 2) 2 3) 3 4) 9
7) The wavelength of electron wave in the first orbit of hydrogen atom is
1) 3.33 A0 2) 0.529 A0 3) 2.21 A0 4) 1.06 A0
Note : Use the formula - n =2 r where r = 0.529 x n2 A0
8) The wavelength of electron revolving in circular orbit in Bohrs atom can be expressed as
nh 2 n2h 2 nh
1) 2
2) 2 2
3) 4) None
2mZe 4 me 2 m
9) The wavelength of electron wave in the 2nd orbit of hydrogen atom is x cm. The wavelength of
electron in the third orbit will be
9x 2x 4x 3x
1) cm 2) cm 3) cm 4) cm
4 3 9 2
10) The relation between wavelength of electron and its kinetic energy is
h nh h h2
1) = 2) = 3) = 4) =
KE KE 2.KE.m 2.KE.m
-11
11) The kinetic energy of electron in an orbit of hydrogen atom is 2.18 x 10 erg. The wavelength of
electron wave will be.
1) 0.529 A0 2) 2.21 A0 3) 3.33 A0 4) None
12) The ratio of wavelengths of electron waves of first three orbits in hydrogen atom is
1 1
1) 1: : 2) 1 : 2 : 3 3) 3 : 2 : 1 4) 1 : 4 : 9
2 3
13) The ratio of radii of two successive orbits is 4 : 9. The ratio of the wavelengths of electron waves in
these orbits is
1) 9 : 4 2) 3 : 2 3) 16 : 81 4) 2 : 3
14) The ratio of wavelengths of electron waves in two orbits is 3 : 5. The ratio of kinetic energies of
electrons will be
1) 25 : 9 2) 5 : 3 3) 9 : 25 4) 3 : 5
15) Moving particles of kinetic energy 13.6 eV are described by waves of length 3.32 Ao. What is the
kinetic energy of same moving particles with twice this wavelength, that is with wavelength 6.64 Ao?
1) 3.4 eV 2) 6.8 eV 3) 13.6 eV 4) 27.2 eV
 10
Heisenbergs uncertainty principle
1) The mathematical expression for Heisenbergs uncertainty principle is
h h2 h h
1) x. v 2) x. p 3) x. p 4) x . m v
n n n
-5
2) Uncertainty in position of a 0.25g particle is 10 m. Uncertainty in velocity will be
1) 1.2 x 1034 m.sec-1 2) 1.6 x 10-20 m.sec-1 3) 1.7 x 10-19 m.sec-1 4) 2.1 x 10-26 m.sec-1
3) Uncertainty in the position of an electron moving with a velocity 300 m.s-1 accurate upto 0.001% will
be
1) 19.3 x 10-2 m 2) 5.76 x 10-2 m 3) 1.93 x 10-2 m 4) 3.84 x 10-2 m
4) If the uncertainty in the location of an electron is 20 pm, then what is the uncertainty in its speed?
1) 1.6 103 ms1 2) 1.4 106 ms1
7 1
3) 1.2 10 ms 4) 2.9 106 ms1

Schrodinger wave equation

1) The Schrodinger wave equation which describes the three dimensional electron wave with potential
energy V is given by
2 2 2 8 2 m
1) E V 0
x 2 y 2 z 2 h

2 2 2 8 m
2) 2 E V 0
x 2 y 2 z 2 h

2 2 2 8 2 m
3) 2 E V 0
x 2 y 2 z 2 h

2 2 2 8 m
4) E V 0
x 2 y 2 z 2 h
2) Choose the incorrect statement
1) is called orbital wave function. It represents the amplitude of electron wave, but has no physical
significance.
2) 2 is called probability density of electron and always has positive values.
3) Schrodingers wave equation is time dependent. 4) None
3) Which of the following is not a boundary condition required to get valid Eigen functions for ?
1) must be finite and continous
2) must be single valued at a given point
3) The probability of finding the electron over the space from + to - must be equal to zero
4) All
4) H in the schrodinger equation, H E ,is known as
1) Kinetic energy operator 2) Heisenberg operator
3) Hamiltonian operator 4) Potential energy operator

Note : The total energy operator also called as Hamiltonian operator is the sum of Kinetic energy operator (T) and potential

energy operator ( V ) . = T + V
i.e., H .

5) The orbital wave function written in terms of polar co-ordinates : r, and can be expressed as

r, , R r
Choose the incorrect statement related to above expression.
 11
1) R (r) is called radial wave function which depends on quantum numbers n & l
2) & are the angular wave functions which depend upon quantum numbers l and m
3) R (r) gives dependence of orbital upon radial distance of electron from the nucleus.
4) and are the angular wave functions and depend only on principal quantum number n
Note : The orbital wave functions ( ) can be expressed in terms of spherical polar co-ordinates (r, & ). The relation
between polar co-ordinates and cartesian co-ordinates can be given as
x = r sin cos
y = r sin sin
z = r cos

6) The energy of quantized energy states in hydrogen atom can be given by

e e 4 e e2 e e4 e e 4
1) En 2) E n 3) En 4) En
8 02 h 2 n 2 4 0 h 2 n 2 2 0 h 2 n 2 8 0 hn
Note : 1) e is called reduced mass of electron

1 1 1

m mn
e e
Where me = mass of electron
mn = mass of nucleus
2) For hydrogen atom electron energy depends only on n and independent of l and n.
7) The probability of finding an electron at a distance r from the nucleus regardless of direction is called
1) radial wave function 2) radial probability density 3) radial probability function 4) All
Note : R = radial wave function
R2 = radial probability density
2 2
4 r drR radial probability function
8) The correct graph of radial wave function (R) of 2s orbital plotted against radial distance r is
 12

Note : Option 1) is the graph for 1s orbital

Option 2) is the graph for 3s orbital
Option 4) is the graph for 2p orbital
9) The maximum electron density can be found at the nucleus in case of orbital
1) s 2) p 3) d 4) none
Note: Consider above graphs of s orbitals. The R value is maximum at r=0. Also consider the R2 vs r graphs in the
following question.
10) The correct graph of radial probability density (R2) of 2p orbital plotted against radial distance r is

Note : Option 1) is the graph for 1s orbital

Option 2) is the graph for 2s orbital
Option 4) is the graph for 2p orbital
11) The correct graph of radial probability function (4 r 2 R 2 ) of 2s orbital plotted against radial distance
r is
 13

Note : 2s orbital has one radial node

12) The space around the nucleus where the 2 > 90% is called
1) atomic orbital 2) nodal region 3) nodal plane 4) All
13) The point at a radial distance from the nucleus where the probability of finding the electron is zero is
called
1) Atomic orbital 2) Nodal point 3) Molecular orbital 4) None
14) The radius of maximum probability for 1s orbital of hydrogen atom is
1) 52.9 pm 2) 105.8 pm 3) 264.5 pm 4) 2.116 pm
15) The radial distance from the nucleus at which the nodal region of 2s orbital of hydrogen atom is
1) 0.529 2) 1.050 3) 2.645 4) 2.116
16) In 2s orbital of hydrogen atom the radial probability function has its maximum value at the radial
distance,
1) 2.645 2) 2.116 3) 0.529 4) 1.058
17) In 2p orbital of hydrogen, the radial probability function has its peak vlaue at the radial distance.
1) 2.645 2) 2.116 3) 0.529 4)1.058
18) Assertion : The energy of 2s orbital will be less than that of 2p orbital even though the radius of
maximum probability for 2s orbital is at 264.5 pm and for 2p orbital is at 211.6 pm.
Reason : There is a small additional maxima at 52.9 pm in case of 2s orbital. Hence the electron in
this orbital penetrates little closer to the nucleus and binds strongly to it than that of 2p orbital.
Choose the correct answer
1) Both A & R are correct ; and R is the correct explanation of A
2) Both A & R are correct ; but R is not the correct explanation of A.
3) A is correct but R is incorrect
4) A is incorrect but R is correct.
19) The number of radial nodes present in a given orbital is equal to
1) l 2) n - l - 1 3) n - 1 4) n - l - 2
Note : Radial node, also called as nodal region or spherical node, does not pass through the nucleus
20) The number of angular nodes present in a given orbital is equal to
1) l 2) n - l - 1 3) n - l 4) n - l - 2
 14
Note : Angular node, also called as nodal plane, passes through the nucleus.
21) The number of radial nodes in 1s orbital is
1) 1 2) 2 3) 3 4) 0

22) The number of radial nodes in 2s orbital is

1) 2 2) 3 3) 1 4) 0

23) The number of angular nodes in 2s orbital is

1) 1 2) 2 3) 3 4) 0
Note: Angular nodes are absent in s orbitals.
24) The number of angular nodes in 2p orbital is
1) 1 2) 2 3) 3 4) 0

Note: p orbitals have only one angular node perpenducular to the axis of orientation of the orbital. For example, px orbital has
one angular node along yz plane.
25) The number of radial nodes in 4p orbital is
1) 1 2) 2 3) 3 4) 4

26) The number of radial nodes and angular nodes respectively present in 4dxy orbital will be
 15
1) 0 & 1 2) 1 & 2 3) 2 & 2 4) 1 & 1

Note: 4d orbital has one radial node. And usually d orbitals have two angular nodes. In case of 4dxy orbital the angular nodes
are present along yz and xz planes.
27) The total number of radial and angular nodes present in a given orbital is equal to
1) n 2) n - l 3) n - l - 1 4) n - 1
28) Which of the following radial distribution graph corresponds to orbital with n = 3, l = 2 ?

29) The orbital with two nodal planes but with no nodal regions is
1) 4d 2) 4s 3) 3d 4) 4f
30) The number of nodal planes in 4f orbital is
1) 1 2) 2 3) 3 4) zero
31) The 2 value is zero along xy and yz planes in a d-orbital. The notation of that d-orbital will be
1) dxy 2) dxz 3) dyz 4) 1 or 3
32) Which of the following orbital belongs to principal quantum level, n = 5?
 16

Electronic configuration
1) The orbital with least energy before filling up of electrons is
1) 3d 2) 4s 3) 4p 4) 5s
Note : Orbital with least (n + l) value has least energy and is filled first
2) The orbital which is filled first will be
1) 4f 2) 5d 3) 6p 4) 7s
Note : If the orbitals possess same (n + 1) value, the orbital with least n value has least energys
3) Which of the following electronic configuration violates Hunds rule
1) 1s 2 2s 2 2 p1x p1y p1z 2) 1s 2 2 s 2 2 px2 p1y pzo 3) 1s 2 2 s 2 2 px2 p 2y p1z 4) 1s 2 2 s 2 2 p1x p1y pz0
4) No two electrons in an atom can have same set of quantum numbers. This statement is known as
1) Hunds rule 2) Heisenbergs uncertainty principle 3) Paulis exclusion principle 4) None
5) The correct ground state electronic configuration of chromium is
1) [Ar] 3d4 4s2 2) [Ar] 3d5 4s2 3) [Ar] 3d5 4s0 4) [Ar] 3d5 4s1
6) The set of quantum numbers of valence shell electron in potassium atom is
1) n = 3, l = +1, m = +1, s = + 1 / 2 2) n = 4, l = 0, m = 0, s = + 1 / 2
3) n = 3, l = 0, m = 0, s = + 1 / 2 4) n = 3, l = l, m = 0, s = + 1 / 2
2 3 1
7) [Ne] 3s 3p 3d is the electronic configuration of
1) P in ground state 2) S in 1st existed state
3) P in 1st excited state 4) S in 2nd existed state
8) The number of electrons in the valence shell of calcium is
1) 2 2) 3 3) 1 4) 6
9) In a multi electron atom, which of the following orbitals described by the three quantum numbers will
have the same energy in the absence of magnetic and electric fields ?
a) n = 1, l = 1, m = 0;
 17
b) n = 2, l = 0, m = 0;
c) n = 2, l = 1, m = 1;
d) n = 3, l = 2, m = +1;
e) n = 3, l = 2, m = 0
The correct combinations are
1) a & b 2) b & c 3) a & d 4) d & e
10) Which orbital is nearest to the nucleus after filling with electrons ?
1) 5d 2) 6s 3) 6p 4) 4f
2+
11) The number of electrons in 3d - orbital in Zn ion is
1) 8 2) 10 3) 9 4) 0
12) The number of electrons with l = l in the ground state of sulfur atom is
1) 6 2) 10 3) 8 4) 4
13) The number of unpaired electrons in 3d orbital of copper atom is
1) 5 2)10 3) 1 4) None
Note: Copper has anomalous electronic configuration i.e., [Ar] 3d104s1
14) The magnetic moment of Mn2+ ion is
1) 3.87 BM 2) 5.9 BM 3) 7.93 BM 4) 6.92 BM
Formula: magnetic moment( )= n(n+2) BM
where n=no. of unpaired electrons

15) The correct increasing order of energy of 4f, 5p, 6s & 5d orbitals is
1) 4f < 5p < 5d < 6s 2) 4f < 6s < 5d < 5p
3) 5p < 6s < 4f < 5d 4) 5p < 5d < 6s < 4f
16) The number of exchanges possible between parallel electrons in d orbitals of chromium is
1) 6 2) 10 3) 5 4) 4
Note: In [Ar] 3d54s1 configuration, there are five unpaired d electrons. The number of exchanges are calculated by following
formula. These exchanges between degenerate d-electrons lower the energy of the atom and thus by confering more stability to
the atom in this anomalous configuration.
If the configuration is [Ar] 3d44s2 as predicted, then the exchanges possible are only 6. Hence this configuration is less stable.

5 5 1 n!
Formula : 5C = 10 this is the modification of equation
2 2! r ! n r !

17) The maximum number of electrons possible in an atom with n = 4 and ms = - 1/ 2 is

1) 32 2) 8 3) 4 4) 16
18) The electronic configuration of hydride ion is
1) 1s1 2) 1s0 3) 1s2 4) 2s1
19) Assertion[A] : [Ar] 3d54s1 configuration of chromium is more stable than [Ar] 3d44s2 configuration
Reason[R] : The exchange energy will be maximum in case of atoms with half filled subshells
1) Both A & R are correct ; and R is the correct explanation of A
2) Both A & R are correct ; but R is not the correct explanation of A.
3) A is correct but R is incorrect
4) A is incorrect but R is correct.
20) Which of the following pairs has two unpaired electrons
1) Mg, Si 2) S, Mg 3) S, Si 4) S, Fe
Atomic structure 1

ATOMIC STRUCTURE

INTRODUCTION
Atom:- The smallest particle which can take part in a chemical reaction with out losing its identity is known
as atom.

Subatomic particles: Electrons, protons and neutrons are known as subatomic particles.

Electron:- The negatively charged fundamental particle present in an atom with negligible mass is called
electron.
The mass of an electron is 1/1836 of mass of proton or hydrogen atom. In atomic mass units it is equal
to 0.000548 amu or 9.1095 X 10-31kg. Its charge is 1.6022 X 10-19coulomb.

Discovery of Electron : -
Sir William Crookes designed a cathode ray discharge tube in which cathode rays are observed only
at very low pressures and very high voltages. These rays consist of negatively charged particles called
electrons.

To vacuum pump

Cathode - + Anode

High voltage

Characteristics of cathode rays : -

1) Cathode rays are not visible but their behavior can be observed with the help of a fluorescent or a
phosphorescent.
2) These rays travel from cathode to anode.
3) These rays travel in straight lines in the absence of electric and magnetic fields.
4) But these rays deflect like negatively charged particles in electric and magnetic fields. Hence the rays
constitute negatively charged particles and are known as electrons.
5) These rays are independent of the nature of the cathode material and nature of the gas present in the
cathode ray tube.
These facts conclude that electrons are the negatively charged fundamental particles present in all the
substances.

Charge to mass ratio of Electron (e/me) : - Charge to mass ratio of electron is calculated by J.J.
Thomson as follows.
e
1.75882 x 1011 C kg 1
me
Charge on the Electron :- The charge on the electron was calculated by Millikan in oil drop experiment
as 1.60 x 10-19 coulombs.
The mass of the electron can be derived as follows.
e
me 9.1094 x 10-31 kg
e / me
Atomic structure 2
Proton:- The positively charged fundamental particle present in the atom is called proton.
The mass of a proton is 1.007277 amu or 1.67252 X 10-27 kg. Its charge is same as that of electron.

Discovery of proton : -
Protons are discovered in canal ray experiment. These rays are produced in modified cathode ray
tube.

Characteristics of canal rays :

1) Canal rays constitute positively charged particles. The characteristics of these rays depend on the nature
of gas present in the cathode ray tube
2. The e/m ratio of the particles depend on the nature of gas taken.
3. Some of the positively charged particles carry a multiple of the fundamental unit of electrical charge.
4. The behavior of these particles in the magnetic or electric field is opposite to that observed for electron.
5. When hydrogen gas is used in the discharge tube, the positively charged particles emitted are found to
possess mass of 1 amu and these are called protons.

Neutron:- The neutral fundamental particle present in the atom is called neutron.
The mass of a neutron is 1.00898 amu or 1.67495 X 10-27kg. It has no charge.
Discovery of neutrons: Chadwick discovered neutrons by bombarding a thin layer of Be with par-
ticles.

Relative
Particle Charge Mass in amu Mass in kg
charge
Electron -1.602 x 10-19 -1 0.000542 amu 9.1 x 10-31 kg
Proton +1.602 x 10-19 +1 1.00727 amu 1.672 x 10-27 kg
Neutron 0 0 1.00867 amu 1.674 x 10-27 kg

Atomic number (Z):-The number of protons or the number of electrons in an atom is called atomic
number. It is represented by 'Z'.
Moseley discovered a simple relation between the frequencies of the characteristic X-rays of an
element and its atomic number.
v = a(Z-b)
= frequency of X-rays
Z = atomic number
a,b are constants which are characteristic of elements

Mass number(A):- The total number of protons and neutrons in an atom is called mass number. It is
denoted by 'A'.
A = no. of protons + no. of neutrons
A = Z + no. of neutrons
no. of neutrons = A - Z

Isotope:- Isotopes are the atoms of an element with same atomic number but differ in their mass numbers
i.e., The isotopes of an element have same number of protons but differ in the number of neutrons.
eg., Hydrogen has three isotopes - Hydrogen(1H1), Deuterium (1H2) and Tritium (1H3). They have same
number of protons (one) but the numbers of neutrons are 1,2 and 3 respectively.

Isobars :- The atoms of different elements with same mass number but different atomic numbers are called
Isobars.
Eg., 6C14, 7N14
Atomic structure 3

Atomic weight:- The atomic weight of an element is the average weight of all the isotopes of that element.
Note:- Atomic number is a whole number but Atomic weight may be a fractional number.

ATOMIC MODELS
J.J.Thomsons model:
According to this model, an atom has a spherical shape in which the positive charge is uniformly
distributed. The electrons are embedded into it in such a manner as to give the most stable electrostatic
arrangement.

Rutherfords planetary model :

Experiment:
A narrow beam of - particles is passed through a thin gold foil which is surrounded by circular
screen made up of fluorescent zinc sulphide. Whenever - particles strike the screen, a tiny flash of
light was produced at that point.

Gold foil

Source of alpha particles Lead plate

Photographic plate

Ruther ford's scattering experiment

Observations:
1) Most of the - particles pass through the foil undeflected.
2) A small fraction of the - particles were deflected by small angles.
3) A very few - particles bounced back i.e. were deflected by 180o.

Conclusions:
1. Most of the space in the atom is empty.
2. The positive charge in the atom is concentrated in the small dense portion called the nucleus.
3. Electrons revolve around the nucleus in circular paths called orbits. It resembles the solar
system.
4. Electrons and the nucleus are held together by electrostatic forces of attraction.

Drawbacks:
1) Rutherfords model could not explain the stability of atom. According to electromagnetic theory,
the charged particle under acceleration should continuously emit radiation. Hence the electron moving in
the orbits must lose energy and fall into the nucleus. But this is not happening.
2) This model could not explain the electronic structure and energy of electrons.
3) It could not explain the atomic spectra.
Atomic structure 4
NATURE OF LIGHT
Light is considered as an electromagnetic radiation. An electromagnetic radiation consists of two
components i.e., Electric component and Magnetic component which are perpendicular to each other as
well as to the direction of path of radiation. The electromagnetic radiations are produced by the vibrations
of a charged particle.

wavelength
E amplitude of electric field
M amplitude of magnetic field

The properties of light can be explained by considering it as either wave or particle as follows.

WAVE NATURE OF LIGHT

By considering light as wave, following properties can be defined for it.
Wavelength: The distance between two successive similar points on a wave is called as wavelength. It is
denoted by .
Units: cm, Angstroms(Ao), nano meters(nm), milli microns(m) etc.,
1 Ao = 10-8 cm.
1 nm= 10-9m = 10-7cm

Frequency: The number of vibrations done by a particle in unit time is called frequency. It is denoted by
'.
'
Units: cycles per second = Hertzs = sec-1.
Velocity: Velocity is defined as the distance covered by the wave in unit time. It is denoted by 'c'.
Velocity of light = c = 3.0 x 108 m.sec-1 = 3.0 x 1010 cm.sec-1
Note: For all types of electromagnetic radiations, velocity is a constant value.
The relation between velocity, wavelength and frequency can be given by following equation.
velocity = frequency x wavelength
c
Wave number: The number of waves spread in a length of one centimeter is called wave number. It is
denoted by
1


units: cm , m-1
-1

Amplitude: The distance from the midline to the peak or the trough is called amplitude of the wave. It is
usually denoted by 'A' (a variable).
Amplitude is a measure of the intensity or brightness of light radiation.

Problems
1) The wave length of a radiation emitted by a sodium lamp is 300 nm. Find its frequency.
2) The frequency of an electromagnetic radiation is 300 Hz. Calculate its wave length.
3) The wave number of a radiation is 9000 cm-1. Calculate its frequency.
4) Calculate the wave number of the yellow light of wave length 600 m emitted from sodium lamp.
Atomic structure 5

PARTICLE NATURE OF LIGHT

Though most of the properties of light can be understood by considering it as a wave, some of the
properties of light can only be explained by using particle (corpuscular) nature of it. Newton considered
light to possess particle nature. In the year 1900, in order to explain black body radiations, Max Planck
proposed Quantum theory by considering light to possess particle nature.

PLANCK'S QUANTUM THEORY

Black body:- The object which absorbs and emits the radiation of energy completely is called a black
body.
Practically it is not possible to construct a perfect black body. But a hollow metallic sphere coated
inside with platinum black with a small aperture in its wall can act as a near black body.
When the black body is heated to high temperatures, it emits radiations of different wavelengths.
Following curves are obtained when the intensity of radiations are plotted against the wavelengths, at
different temperatures.

classical theory
7000 K
intensity

5000 K

wavelength

Following conclusions can be drawn from above graphs.

1. At a given temperature, the intensity of radiation increases with wavelength and reaches a maximum
value and then starts decreasing.
2. With increase in temperature, the wavelength of maximum intensity ( max ) shifts towards lower wave-
lengths.
According to classical physics, energy should be emitted continuously and the intensity should in-
crease with increase in temperature. The curves should be as shown by dotted line.
In order to explain above experimental observations Max Planck proposed following theory.
1. Energy is emitted due to vibrations of charged particles in the black body.
2. The radiation of energy is emitted or absorbed discontinuously in the form of small discrete energy
packets called quanta.
3. Each quantum is associated with definite amount of energy which is given by the equation E=h

Where
h = planck's constant
= 6.625 x 10-34 J.sec
= 6.625 x10-27 erg.sec
= frequency of radiation
Atomic structure 6
4. The total energy of radiation is quantized i.e., the total energy is an integral multiple of h . It can only
have the values of 1 h or 2 h or 3 h . It cannot be the fractional multiple of h .
5. Energy is emitted and absorbed in the form of quanta but propagated in the form of waves.

EINSTEIN'S GENERALIZATION OF QUANTUM THEORY

Einstein generalized the quantum theory by applying it to all types of electromagnetic radiations. He
explained photoelectric effect using this theory.

Photoelectric Effect:- The ejection of electrons from the surface of a metal, when the metal is exposed to
light of certain minimum frequency, is called photoelectric effect.
The frequency of light should be equal or greater than a certain minimum value characteristic of the
metal. This is called threshold frequency.
Photoelectric effect cannot be explained by considering the light as wave.
Einstein explained photoelectric effect by applying quantum theory as follows,
1. All electromagnetic radiations consists of small discrete energy packets called photons. These photons
are associated with definite amount of energy given by the equation E=h .
2. Energy is emitted, absorbed as well as propagated in the form of photons only.
3. The electron is ejected from the metal, when a photon of sufficient energy strikes the electron.
When a photon strikes the electron, some part of the energy of photon is used to free the electron
from the attractive forces in the metal and the remaining part is converted into kinetic energy.
h = W + K.E
where
W = energy required to overcome the attractions
K.E = kinetic energy of the electron

Problems
1) Calculate the energy of one photon of radiation whose frequency is 3x1012 Hz.
2) The energy of a electro magnetic radiation is 6.625x10-19 J Calculate The Wavelength of radiation.

SPECTRA
When electromagnetic radiation is passed through a prism or grating it is splitted and forms a collec-
tion of lines representing different wavelengths. This is called spectrum.
Spectra can be divided into two types viz., emission and absorption spectra as given below.

Emission Spectra Absorption Spectra

1) These are obtained due to emission of radiation These are obtained when substance absorb the
from the substances. radiation.
2) White lines are formed on the black back ground. Black lines are formed on the white back ground.

3)These are formed when atoms or molecules are de-These are formed when atoms or molecules are
excited from higher energy level to lower energy excited from lower energy level to higher energy
level. levels.

Spectra can also be divided into line and band spectra as given below.

Line Spectra Band Spectra

1) It consists of sharp and well defined It consists of closely spaced lines
lines. called bands.
2) Characteristic of atoms Characteristic of molecules.
3) Formed due to the excitation and de- Formed due to the vibrations and
excitation of electrons in the atoms. rotations of atoms in molecules.

4) It is also known as atomic spectra It is also known as molecular spectra

Atomic structure 7
HYDROGEN ATOMIC SPECTRUM
A bright light is emitted when a high potential is applied to hydrogen gas at low pressure in a discharge
tube. This bright light is dispersed and forms a spectrum upon passing through a prism or grating. The
spectrum consists of separate lines corresponding to different wavelengths. This is called Hydrogen atomic
spectrum.
The spectral lines are formed due to electronic transitions from one energy level to another. These
lines are divided into five series according to the range of wavelengths as follows.

Spectral series Spectral region n1 n2

1. Lyman series
2. Balmer series
3. Paschen series
4. Brackett series
5. Pfund series
Ultra-violet 1 2,3,4,5,6,7,_ _ _ _
Visible 2 3,4,5,6,7,_ _ _ _
near infra-red 3 4,5,6,7,_ _ _ _
infra-red 4 5,6,7,_ _ _ _
far infra-red 5 6,7,_ _ _ _

n1and n2 are the principal quantum numbers of the energy levels.

The wave numbers of spectral lines in each series can be calculated using Rydberg's equation as follows.
1 1
RH Z 2 2 - 2
n1 n2
where
n1and n2 are the principal quantum numbers of orbits corresponding to electronic transition.
RH = Rydberg's constant = 1,09,677 cm-1
Z = atomic number

n=7
n=6
n=5
Pfund
n=4
Brackette
n=3
Paschen

n=2
Balmer

n=1
Lyman

Note: Every element has its own characteristic line spectrum. There is regularity in the line spectrum of each
element. Hydrogen has the simplest line spectrum among all the elements. The line spectra become com-
Atomic structure 8
plex with increase in atomic number of the element.

Problems
1) An electronic transition from n=3 to n=1 shell takes place in a hydrogen atom. Find the wave number
and the wave length of radiation emitted. [Given R=1,09,677 cm-1]

BOHR'S ATOMIC MODEL

In order to explain the Hydrogen atomic spectrum, Bohr proposed following atomic model based on
quantum theory.

MAIN POSTULATES OF BOHR'S ATOMIC THEORY

1. The electrons in an atom revolve around the nucleus in definite closed circular paths called orbits (energy
levels or states or shells).
2. The orbits are represented by principal quantum number 'n'. These are numbered 1,2,3,4 _ _ _ (or
K,L,M,N,_ _ _) from the nucleus.
3. The energy of an electron in a particular orbit is constant and the electron neither emits nor absorbs
energy as long as it revolves in the orbits. Hence these orbits are called stationary orbits.

n=3
n=2
n=1

Nucleus

4. The angular momentum of electron is quantized.

nh
angular momentum = mvr =
2
Where
m = mass of an electron
v = velocity of an electron
r = radius of orbit
h = Planck's constant
= 6.625 X 10-34 J.sec
= 6.625 X 10-27 erg.sec
n = principal quantum number which can have only positive integer values(1,2,3,4 _ _ _).
The electron revolves only in those orbitals where the angular momentum of it is the integral multiple
h h h h
of i.e, 1 or 2 or 3 ___
2 2 2 2
5. Each orbit is associated with definite amount of energy and radius. The energy of the orbit (and of
electron in it) increases with increase in the radius of the orbit. Thus farther the orbit from nucleus greater is
the energy.
6. The energy of an electron changes when it moves from one energy level to another.
Energy is absorbed when the electron jumps from lower orbit to higher orbit. Whereas energy is
emitted when the electron jumps from higher orbit to lower orbit.
The energy absorbed or emitted during electronic transitions between two orbits is equal to the
Atomic structure 9
energy difference between these orbits. It is given by
E = E2 - E1
The energy released in the form of radiation will appear as a spectral line in the atomic spectrum.

DERIVATION OF EXPRESSIONS FOR RADIUS OF ORBIT AND ENERGY OF ELECTRON

Radius of Orbit
In hydrogen atom, there is one proton in the nucleus, and an electron revolving around the nucleus in
a circular orbit of radius 'r'. Let
the charge on proton = +e
the charge on electron = -e.

Centrifugal force

-e

+e

The attraction between the nucleus and electron acts centripetally towards the nucleus. As per
Coulomb's law,
e 2
force of attraction =
r2
There is also centrifugal force acting away from the nucleus due to the revolving of electron in the
orbit.
mv 2
centrifugal force =
r
where
m = mass of electron,
v = velocity of electron
During the orbiting of electron in a stationary orbit, these two forces must be equal.
e 2 mv 2
i.e., 2 =
r r
e2
or mv 2 --------- 1
r
According to Bohr's theory, Angular momentum of electron in an orbit is given by
nh
mvr
2
nh
or v
2 mr
n2h2
or v2
4 2 m 2 r 2
By substituting the value of v2 in equation-1
Atomic structure 10

e2 mn 2 h 2
2 2 2
r 4 m r
n2h2
or r ------------- 2
4 2 me 2
By substituting the values of
planck's constant = h = 6.625 x 10-27erg.sec
mass of electron = m = 9.1 x 10-28 g
charge on electron = e = 4.802 x 10-10 e.s.u
radius of nth orbit = r = 0.529 x 10-8 x n2 cm

Energy of Electron
The total energy of electron is equal to the sum of Kinetic and Potential energies.
i.e., Total Energy (T.E) = Kinetic Energy (K.E) + Potential Energy (P.E)
1 1 e2 e2
where K.E = mv 2 (since mv 2 from equation 1)
2 2 r r
e2
and P.E =
r
e2 e2
Hence T .E
2r r
e2
T .E
2r
Upon substituting the value of 'r' from equation-2
2 2 me 4
T .E 2 2
nh
By substituting the values of constants, the energy of electron (En) in the nth orbit can be written as

21.7 x10-12
En erg per atom
n2
21.7 x10-19
Joule per atom
n2
21.7 x10-22
kJ per atom
n2

EXPLANATION OF HYDROGEN ATOMIC SPECTRUM

Bohr could successfully explain the hydrogen atomic spectrum using his postulates as given below.
The energy of an electron in hydrogen atom is given by
2 2 me 4 1
En . 2 (1)
h2 n
2 2 me 4 1
Therefore E1 . 2
h2 n1
Atomic structure 11

2 2 me 4 1
E2 . 2
h2 n2

2 2 me 4 1 2 2 me 4 1
And E2 E1 . 2 . 2
h2 n2 h2 n1

2 2 me 4 1 1
Therefore E2 E1 2 2 (2)
h2 n1 n2
According to Bohrs postulates,
E2 E1 h
But c
Therefore E2 E1 hc

2 2 me4 1 1
Hence 2 2 2 hc
h n1 n2

1 2 2 me 4 1 1
or 2 2 (3)
ch3 n1 n2
This equation is similar to Rydbergs equation
1 1 1
RH 2 2
n1 n2

2 2 me 4
Where RH is equal to and its value can be determined by substituting the following values.
ch 3
m=9.1 x 10-28 g, e = 4.8 x 10-10 e.s.u.
= 3.14, c = 3 x 1010 cm, h = 6.626 x 10-27 erg. sec
2 2me4
RH = 3
1,09,681cm 1
ch
Above value is almost equal to Rydbergs constant (RH = 1,09,677 cm-1). The frequencies of spectral
lines in hydrogen atomic spectrum can also be determined by using Bohrs theory.

MERITS AND DEMERITS OF BOHR'S ATOMIC THEORY

Merits
1. This theory successfully explained the spectra of mono-electronic species like Hydrogen, He+, Li2+, Be3+
etc., .
2. Bohr successfully calculated the frequencies of spectral lines, radii and energies of orbits which are in
excellent agreement with experimental results.

Demerits (defects)
1. Bohr's atomic model is a flat model. But atoms are spherical.
2. This theory could not explain the spectra of atoms containing multi-electrons.
3. It was shown later on that the each spectral line in hydrogen atomic spectrum was actually closely
spaced group of fine lines. These fine lines were revealed when the spectrum was taken on high resolution
spectrometer in later years. Bohr could not explain this fine spectrum.
Atomic structure 12
4. Splitting of spectral lines when the atoms are placed in strong magnetic field is called Zeeman effect.
Splitting of spectral lines when the atoms are placed in strong electric field is called Stark effect.
Bohr could not account for these effects.
5. According to Heisenberg's uncertainty principle, it is not possible to calculate the velocity and position of
an electron accurately and simultaneously. But Bohr calculated them. This is a contradiction.
6. According to De Broglie's wave concept, electron has wave nature. But Bohr's theory considered
electron as a particle.

QUANTUM NUMBERS
Quantum numbers are the numbers used to describe the position and energy of an electron in an
atom. There are four types of quantum numbers.

i) Principal quantum number

ii) Azimuthal quantum number
iii) Magnetic quantum number
iv) Spin quantum number

Principal quantum number (n)

1. Principal quantum number was proposed by Bohr to explain the hydrogen atomic spectrum
2. It denotes the main energy level (or shell or orbit).
3. It is denoted by 'n'. It can have positive integral values from 1,2,3,4,_ _ _ (or K,L,M,N_ _ _ ).
4. It also describes the energy and size of the orbit. The energy and the size of orbit increases with increase
in 'n' value.
5. The maximum number of electrons that can be accommodated in a given shell is equal to 2n2 .

Azimuthal quantum number (l)

1. Azimuthal quantum number was proposed by Sommerfield in order to explain the fine hydrogen atomic
spectrum.
2. It denotes the sub-levels (or sub-shells) in the atom. It is denoted by 'l'
3. The number of sub-levels in a given main energy level is equal to the principal quantum number 'n'. These
sub-levels are indicated by azimuthal quantum number 'l' which can have values from 0 to n-1.
For ex: In an orbit of principal quantum number n=3, there are three sublevels denoted by l =0,1 and 2.
4. Azimuthal quantum number also describes the angular momentum of electron and shape of orbitals
present in that sublevel.
For ex:
l = 0 (s)--- spherical
l = 1 (p)--- dumbbell
l = 2 (d)--- double dumbbell

Magnetic quantum number (m)

1. Magnetic quantum number was proposed by Lande in order to explain the Zeeman and Stark effects.
The splitting of spectral lines in strong magnetic field is called Zeeman effect and splitting in strong
electric field is called Stark effect.

2. It is denoted by 'm'. It describes the orientation of orbitals.

3. The number of orientations possible for orbitals in a given sublevel 'l' is equal to the (2l+1) and can have
values from -l_ _ _ 0 _ _ _+l.
For ex: The number of orientations (m values) possible for a sublevel l=2 is (2X2)+1 = 5 and the values of
m = -2,-1,0,+1 and +2.
Atomic structure 13

Prinicipal quantum number Azimuthal quantum number Magnetic quantum number

(n) (l) (m)
n=1 l=0 m=0
n=2 l = 0,1 m = -1,0,+1
n=3 l = 0,1,2 m = -2,-1,0,+1,+2

Spin quantum number (s)

1. It was proposed by Goudsmit and Uhlenbeck to explain the double line structure of alkali metal spectra.
2. Spin quantum number denotes the spin of the electron on its own axis. It is denoted by 's'. It can have
only two values(+ and -).
3. The clockwise spin is indicated by + or upwards arrow( ) and anti-clockwise spin by - or down-
wards arrow( ).

Quantum number Possible values Significance

1. Prinicipal quantum number (n)
2. Azimuthal quantum number (l)
3. Magnetic quantum number (m)
4. Spin quantum bumber (s)
1,2,3,4_ _ _ _ _ Denotes the size and energy
of orbit.
0 to n-1 Denotes the sub-level and
shapes of orbitals in that sub-
level. It indicates the angular
momentum of electron.
-l _ _ _0_ _ _+l Indicates the spatial
orientation of orbital.
+1/2 or -1/2 Denotes the spin of electron.

Problems
1) What is the shape of orbital if the quantum numbers for the electron in it are n = 3, l = 2, m = -1, and
s = +1/2
2) Which of the following set of quantum numbers is not possible?
a) n = 3, l = 2, m = -2, s = +1/2
b) n = 2, l = 2, m = -1, s = +1/2
c) n = 4, l = 3, m = 0, s = +1/2
d) n = 3, l = 1, m = -2, s = +1/2
3) How many electrons in an atom may have the quantum numbers, n = 3 and ms= -1/2 ?
4) How many sub-shells, orbitals and electrons are present in n = 3 main shell?

DE BROGLIE'S WAVE CONCEPT

According to de Broglie, every particle in motion is associated with wave nature. The wavelength
( ) of every particle wave can be expressed by the following equation.
h h
(or)
p mv
where
h = Planck's constant
m = mass of the particle
v = velocity of the particle
p = mv = momentum of the particle
Atomic structure 14
Derivation
According to Einstein, mass and energy equivalence can be expressed as
E = mc2
According to Planck's quantum theory,
E h
Hence
mc 2 h ------------ 1
But
c
or
c


By substituting the value in the 1st equation

hc
mc 2

or
h h
(or)
mc p
where
p = momentum of a photon
de Broglie proposed that above equation is applicable to every particle in motion and above equation
can be written as

h h
v
m p
The wavelengths of macro bodies like cricket ball or stones are very small as their masses are large
and hence can be ignored. But for micro particles like electrons, the wavelengths are considerable.

JUSTIFICATION OF BOHR'S CONCEPT

According to de Broglie, electron in an atom is considered as a standing or stationary wave, which
revolve around the nucleus in a circular orbit. In order to behave as a stationary and non-energy radiating
wave, the electron wave must be in phase i.e., the two ends of the wave must meet at one place and there
should be constructive interference of crests and troughs.

Wave in phase - constructive Wave out of phase

inter ference destructive inter ference

To satisfy this condition, the circumference(2 r) of the orbit must be equal to the integral multiple of
the wavelength( ) of the electron wave.
i.e., n 2 r
Atomic structure 15
2 r
or where 'n' is an integer
n
But according to de Broglie's theory
h

mv
Hence
2 r h

n mv
nh
or mvr
2
This is Bohr's equation. According to Bohr's theory, the angular momentum (mvr) of electron revolv-
h
ing in a stationary orbit is an integral multiple of i.e., angular momentum is quantized.
2
But when the 'n' is not an integer, there is destructive interference and the wave will go out of phase.
This results in loss of energy by the electron wave.

Problems

8) What will be the wavelength of a ball of mass 0.1 Kg moving with a velocity of 10 m/sec.
9) The mass of an electron is 9x10-31 kg and its velocity is 930 m/sec.Calculate its wave length.
10) Calculate the momentum of particle whose de Broglie wavelength is 2A0.

HEISENBERG'S UNCERTAINTY PRINCIPLE

According to Heisenberg, it is impossible to calculate the position and momentum of micro particles
like electrons accurately and simultaneously.
x) and momentum( p) is always equal to
Mathematically, the product of uncertainties in position(
h
or greater than
n
h
x.p
n
where
x = uncertainty in position
p = mv = uncertainty in momentum
m = mass of the particle
v = uncertainty in velocity
h = planck's constant
n = 1,2,3,4,......
For an electron n 4
Hence we can write
h
x.p for an electron
4

h
or x.v ( p = mv )
4 m
Atomic structure 16
Explanation
Case-1
When the position is calculated accurately, x = 0
then p becomes infinity
i.e., it is not possible to calculate the momentum accurately
Case-2
When the momentum is calculated accurately, p = 0
then x becomes infinity
i.e., it is not possible to calculate the position accurately.

Problems
11) Calculate the uncertainty in the position if the uncertainty in its velocity is 5x105 m/sec for an electron.
12) Calculate the uncertainty in the velocity if the uncertainties in its position is 1A0 for an electron.
13) The uncertainties in the position and velocity of a particle are respectively 1x10-12m and 3x10-24 m/sec.
Calculate the mass of the particle.

QUANTUM MECHANICAL MODEL OF ATOM

SCHRODINGER'S WAVE EQUATION

The important consequence of Heisenberg's uncertainty principle is - it is not possible to determine
the exact position of an electron in an atom. But it is possible to predict the probability of finding an electron
in space around the nucleus. To determine the probability of finding an electron, Erwin Schrodinger pro-
posed wave mechanical model for the motion of electron. He considered electron as a three dimensional
wave moving in the electric field of a positively charged nucleus. He derived an equation which describes
the motion of an electron wave along the three axes x, y and z as follows
2 2 2 8 2 m
2 E V 0
x 2 y 2 z 2 h
In the above equation,
m = mass of electron
E = total energy of electron
V = potential energy of electron
= wave function

Meaning and significance of and 2

:- It is called wave function. It denotes the amplitude or intensity of the electron wave.
2:- It is called probability function. It denotes the probability of finding an electron in space at a given
point.

When Schrodingers wave equation is solved for hydrogen atom, the solutions give possible energy
levels and corresponding values for the electrons. But the accepted solutions to wave functions, which
are called eigen wave functions, are obtained by applying following boundary conditions.
Boundary conditions
1) must be continuous.
2) must be finite.
3) must be single valued at any point.
4) The probability of finding the electron over the space from + to - must be equal to one.
Atomic structure 17
Important features of quantum mechanical model of atom
1) The energy of an electrons in an atom is quantized.
2) The quantized energy levels of electrons are derived from the accepted solutions of Schrodingers wave
equation by considering electron as a wave.
3. All the information about electron in an atom is contained in its orbital wave function .
4. The path of the electron can never be determined accurately. Therefore we find only the probability of
the electron at different points in space around an atom.
5. The probability of finding an electron at a point within an atom is proportional to the square of the orbital
wave function ( 2 ) at that point. 2 is known as probability density and is always positive.
It is possible to predict the region around the nucleus in this region 2 has maximum values. Which is
called atomic orbital, from the 2 values.

SHAPES OF ATOMIC ORBITALS

Atomic orbital:-The space around the nucleus where the probability of finding electron is maximum
( 2 > 95%) is known as atomic orbital.
The shapes of atomic orbitals can be known by solving the Shrodinger's wave equation for 2 values
at different points in the space around the nucleus.

Radial Probability Function (D-function):- The function which denotes the probability of finding an
electron in small volume at a radial distance from the nucleus, without any reference to its direction, is
known as radial probability function or D-function.
D 4 r 2 dr. 2

Nodal Plane:- The plane where the probability of finding the electron is zero ( 2 = 0) is known as nodal
plane.
The nodal plane passes through the nucleus and hence is also known as angular node.
The number of nodal planes for a given orbital = l (azimuthal quantum number)
The number of nodal planes for different orbitals are as follows,

Orbital 'l' no. of nodal planes

s 0 0
p 1 1
d 2 2
f 3 3

Nodal region:- The region around the nucleus where the probability of finding the electron is zero
( 2 = 0) is known as nodal region.
The nodal region does not pass through the nucleus and hence known as radial node.
The number of nodal regions for a given orbital = n - l - 1
For example, the number of nodal regions
for 1s orbital = 1-0-1 = 0
for 2s orbital = 2-0-1 = 1
for 2p orbital = 2-1-1 = 0
Note:-The total of no. of nodal planes and regions for a given orbital = n - l

Radial Probability Distribution curves:- The graphs plotted between the D-function and the radial
Atomic structure 18
distance from the nucleus are known as radial probability distribution curves. These curves give an idea
about the variation of electron density with radial distance around the nucleus for a given orbital.

s-orbital
s-orbitals are spherical in shape with spherical symmetry.
There are no nodal planes for s-orbitals.
The nodal regions for s-orbitals are given as follows
orbital no. of nodal regions
1s 0
2s 1
3s 2
The radial probability curves and shapes of 1s and 2s orbitals are given as follows.

radial distance
Radial probability distribution curve and shape of 1s orbital

radial node

radial distance
Radial probability distribution curve and shape of 2s orbital

p-orbitals
The p-orbitals are double dumbbell in shape.
Each p-orbital contains a nodal plane.
The shapes and orientations of p-orbitals in a given sub level along with the nodal planes are shown as
follows.

x-axis x-axis x-axis

z-axis z-axis z-axis

y-axis y-axis y-axis

radial distance
px py pz

Radial probability distribution curve for 2p orbitals

Atomic structure 19
d-orbitals
The d-orbitals are double dumbbell in shape.
There are two nodal planes for every d-orbital
In a given sub level, there are five degenerate d-orbitals. These are divided into two groups based on
their orientation i.e., t2g group and eg group.

The lobes of d-orbitals in t2g group are oriented in between the axes by making 450 of angle with

them. There are three t2g orbitals i.e., dxy, dxzand dyz.
Where as the lobes of d-orbitals in eg group are oriented along the axes. There are two such eg
orbitals i.e., d x 2 y2 and d z 2 .
In case of d z 2 orbital, there are only two lobes oriented along the z axis and there is a concentric ring
called torus along the xy axes.

x-axis x-axis

z-axis
y-axis y-axis

dxy d x2 y2 d z2

ELECTRONIC CONFIGURATION IN MULTI-ELECTRON ATOMS

Representation of electronic configuration

The electronic configurations of atoms are represented by two methods i.e., nlx method and box
method

nlx method
'n' is principal quantum number
'l' is azimuthal quantum number, indicated by letters s,p,d,f....
'x' is the number of electrons in the orbital
For example, the electronic configuration of 'He' atom can be represented as 1s2.
Here, 'l' is principal quantum number, 's' represents azimuthal quantum number, l = 0 and the super-
script 2 represents the number of electrons present.

Box method
In this method, the orbitals are represented by boxes and the electrons are denoted by upward and
downward arrows in the boxes.
For example, the electronic configuration of 'He' can be represented as follows.

1s2

Principles and rules: The following principles and rules are used in writing the electronic configurations.
Atomic structure 20
Pauli's Exclusion Principle: No two electrons in an atom can have same set of quantum numbers.
For example, the electronic configuration of 'He' is 1s2
The set of quantum numbers of two electrons in 'He' atom are
For first electron, n = 1, l = 0, m = 0, s = +1/2
For second electron, n = 1, l = 0, m = 0, s = -1/2

Aufbau Rules
The electrons in an atom are arranged according to aufbau rules. According to these rules, the differ-
entiating electron in an atom enters into the orbital with lowest energy. The relative energy of an orbital can
be decided from following rules.
1. The orbital with least (n + l) value possesses lowest energy.
For example, the (n + l) values of 1s and 2s orbitals are
for 1s, n + l = 1 + 0 = 1
for 2s, n + l = 2 + 0 = 2
Hence 1s orbital has lower energy than 2s, as it has low n + l value, and the electron will first enter into
1s orbital.
2. If two are more orbitals possess same (n + l) value, the orbital with lower 'n' value has low energy.
For example, the (n + l) values of 2p and 3s orbitals are same
for 2p, n + l = 2 + 1 = 3
for 3s, n + l = 3 + 0 = 3
But 2p orbital with lower 'n' value (=2) possesses lower energy and hence the electron enters first into
this orbital.

Hund's Rule of Maximum Multiplicity: No pairing of electrons occur until all the degenerate orbitals in
an atom are filled with one electron each.
For example, the electronic configuration of carbon is 1s2 2s2 2px1 2py1

1s2 2s2 2px12py1

In above case, the differentiating electron is entering into the 2py orbital instead of 2px because both 2px and
2py orbitals are degenerate orbitals. Hence no pairing occured.

Anomalous electronic configuration

Chromium and copper exhibit anomalous electronic configurations as the atoms with half filled or full -
filled d-orbitals are more stable.

Cr (Z =24) has [Ar] 3d5 4s1 configuration instead of [Ar] 3d4 4s2 as the half filled d-sub level is more
stable.

Cu (Z =29) has [Ar] 3d10 4s1 configuration instead of [Ar] 3d9 4s2 as the full filled d-sub level is more
stable.

Problems
1) Arrange the electrons, for which the quantum numbers are given below, in their increasing order of
energy.
a) n = 3, l = 1, m = -1, s = +1/2
b) n = 4, l = 0, m = 0, s = -1/2
c) n = 3, l = 2, m = -2, s = -1/2
d) n = 5, l = 3, m = +2, s = +1/2
 Prepared by Aneesh Damodaran

X-RAY DIFFRACTION AND BRAGGS EQUATION

1) The diffraction of barium with X - radiation of wavelength 2.29A0 gives a first order diffraction at
300. What is the distance between diffracted planes ?
1) 2.29 A0 2) 2.73 A0 3) 4.58 A0 4) None
Formula : n=2d sin

2) At what angles for the first order diffraction, spacing between two planes respectively are and ?
2
1) 900 & 300 2) 300 & 900 3) 900 & 00 4) 00 & 900
3) An X - ray beam of wavelength 71pm was scattered by a solid. The angle of diffraction (2 ) for a
second order reflection is 1506. The inter planar distance in the crystal will be
1) 710 pm 2) 559 pm 3) 142 pm 4) 71 pm
4) The interplanar distance in a crystal used for X-ray diffraction is 0.2nm. The angle of incidence ( )
of X-rays is 90. If the diffraction is of first order, Find the wavelength of the X-rays.
1) 0.062 nm 2) 0.23nm 3) 0.43nm 4) 0.11nm
5) A first order diffraction of an X-radiation by crystal planes, separated by a distance of 231 pm, in a
solid is observed at a reflection angle of 300. By using same radiation the first order diffraction is
observed at 600 in another solid. The interplanar distance in the second solid will be
1) 462 pm 2) 400 pm 3) 115.5 pm 4) 322 pm
6) A first order diffraction by a crystal plane is observed at an angle of 150. by using x - rays of
wavelength of 258 pm. If the interplanar distance is 500 pm, the second order of diffraction will be
observed at
1) 7.280 2) 10.50 3)31.170 4) 9.20

KEY
1) 1 2) 2 3) 2 4) 1 5) 2 6) 3
 CHEMICAL KINETICS
Rates of reaction
Change in concentration of any of the reactants or products in unit time.
Change in conc. of any reactant or product
Rate of reaction =
Time interval
Expression of average rate of reaction
For a reaction A + B C + D
A B C D
The rate of reaction =
t t t t
For the reaction xA + yB mC + nD
To rationalize the rate of reaction each expression is divided by number of molecules of that substance in equation.
A B C D
So rate of reaction =
xt yt mt nt
Unit of rate of reaction moles L1 S1 or moles L1 min1 or atm S1 or atm min1.

Rate of reaction at a given time or instantaneous rate of reaction

For a reaction xA + yB mC + nD
dA dB dC dD
Rate of reaction at a given time t =
xdt ydt mdt ndt
Factors effecting the rate of reaction
(1) Nature of reactants
(2) Temperature With increase in temperature rate of reaction increases, for every 10 o rise in temperature, the rate
of reaction is almost doubled.
(3) Concentration Higher is the conc. of reactants higher will be rate of reaction.
(4) Catalyst In presence of a catalyst rate of reaction increases.
(5) Surface area of reactants Larger is the surface area of reactants higher will be the rate of reaction.

Rate law expressions

This expression shows the dependence of rate of reaction on concentration terms of reactants as determined
experimentally. The concentration terms may or may not agree with terms given in the reaction. For a reaction
xA + yB mC + nD
According to rate law expression
Rate of reaction [C]a [B]b
Or Rate of reaction = K [C]a [B]b
K = specific rate constant or velocity constant
Velocity constant is the rate of reaction when conc. of all the reactants are taken in unity.

Simple reaction & Complex reaction

Rate law expression for some complex reactions
(1) Thermal decomposition dinitrogen pentoxide:
2N2O5 4NO2 + O2
The mechanism of the reaction is :
Step-I N2O5 NO2 + NO3 (slow)
Step-II N2O5 + NO3 3NO2 + O2 (fast)
Applying law of mass action to the slow step.
Rate of reaction [N2O5]
So rate law is
Rate of reaction = K[N2O5]

(2) Decomposition of ozone

2O3 3O2
The mechanism of the reaction is
1
Step-I O3 O2 + O (fast)
Step-II O + O3 2O2 (slow)
Applying law of mass action to slow step
Rate of reaction [O] [O3].(i)

But O is not the actual reactant, so its concentration is taken in terms of O2 from step I.
Applying law of chemical equilibrium to step-I
K= 2
O O
O3
So [O] = K
O3
O2
Substituting the value of [O] in eq. (i)
Rate of reaction 3
O O3
O2
Rate of reaction = K [O3]2 [O2]-1

(3) For the reaction A2 + B2 2AB

Step I A2 2A (fast)

Step II A + B2 AB + B (slow)
Applying law of mass action to slow step
Rate of reaction [A] [B2](i)
As A is not the reactant, so its concentration is taken in terms of A2 from step-I.
Applying law of chemical equilibrium to step-I
A2
K=
A2
Or [A] = K [ A2 ] (ii)
Applying the value of [A] from eq (ii) in eq (i)
Rate of reaction A2 B2
Order of reaction
Rate of reaction = K [C]a [B]b
So order of reaction = a + b

Molicularity of a reaction:

Modification of Rate law expression

If for a reaction xA + yB products
If rate law expression is
Rate of reaction = K [A]m [B]n
Order of reaction = m + n
If one of the reactants i.e. B is taken in large excess then its conc. is eliminated from the rate law, which may be written as
Rate of reaction = K [A]m [modified rate law expression].
So order of reaction = m

Pseudo unimolecular reactions

Some reactions which have molecularity greater than one but follow the kinetics of 1 st order reaction are known as pseudo
unimolecular reaction.

Units of rate constant or Specific reaction rate for different order reactions.
For a reaction of nth order

2
 dx
Rate, = K [conc.]n.
dt
Or K =
dx

1

1 conc. = 1
dt conc. conc. time time conc.n1
n n

Integrated rate equations

Zero order reaction:
[ R]0 [ R]
K=
t
Taking this equation as equation of straight line if we plot [R] against time, we get a straight line with slope = -K and
intercept = [R]0

1st order reaction

1
R
0
K = 2.303 log
t R
If we consider the conc. of reactants [R]1 and [R]2 at time t1 and t2.

Half life of a reaction

Half life of a zero order reaction
1[ R]0
[K] =
2
Half life of a 1st order reaction
0.693
t1/2 =
K

Relation between half life period & initial conc. of reactants for nth order reaction.
1
t1/2
[ R ] 0n 1
where [R]0 = initial conc. of reactant and n = order of reaction.
Amount of a substance left after nth half life periods for a 1 st order reaction.
initial amount
Amount of reactant left = , where n = number of half-lives.
2n

Examples of 1st order reactions

(1) Decomposition of nitrogen pentoxide
2N2O5 4NO2 + O2
2.303 V
K= log
t V Vt
(2) Decomposition of Ammonium nitrite
NH4NO2 (aq) 2H2O + N2
2.303 V
K= log
t V Vt
(3) Decomposition of H2O2
H2O2 H2O + O
2.303 V
K= log 0
t Vt
(4) Hydrolysis of ester in acidic medium

3

CH3COOC2H5 + H2O H
CH3COOH + C2H5OH
2.303 V V0
K= log
t V Vt
(5) Inversion of canesugar

C12H22O11 + H2O C6H12O6 + C6H12O6
H

Sucrose Glucose Fructose

+66.5o +52.5o -92o
2.303 r r
K= log 0
t rt r
Determination of order of reaction
(1) On the basis of units of K.
(2) On the basis of relation between t1/2 and initial conc. of reactants.
(3) Graphical method:
(4) Initial rate method:

Collision theory of chemical reactions

All the molecular collisions are not effective, only those molecular collisions are effective in which colliding molecules
have
(i) Proper orientation
(ii) Energy = certain minimum energy which is known as threshold energy or critical energy.

Progress of a chemical reaction

(a) Exothermic reaction:
Ea = Activation energy which is the additional energy required by the molecules of reactants, so that their energy
becomes equal to threshold energy and they undergo effective molecular collision to give activated complex and then
products.
Ea = Threshold energy or energy of activated complex or energy barrier average energy of reactants.
Higher is the value of Ea, smaller number of molecules will cross the energy barrier and rate of reaction will be slower. If
Ea has small value then larger number of molecules will cross the energy barrier and rate of reaction will be higher.
For an exothermic reaction Ea has small value and
Ea (forward reaction) + H = Ea (reverse reaction)

(b) Endothermic reaction:

In endothermic reaction Ea (forward) has a large value, larger than H
Ea (forward) = H + Ea (reverse)

Effect of catalyst on the rate of reaction

In presence of a catalyst a new reaction path is developed with low Ea so larger number of molecules will cross the
energy barrier and rate of reaction will increase.

Effect of temperature on the rate of a reaction (Arrhenius Equation)

The rate of reaction increases with increase in temperature. The rate of reaction is almost doubled for every 10 o rise in
temperature.
Rate of reaction at T 10 K
Temperature co-efficient =
Rate of reaction at T K
The value of temperature co-efficient is 2 -3.
The effect of change in temperature on the rate of reaction is given by Arrehenius equation.
K = A e-Ea/RT. Where A = frequency factor, K = velocity constant
Ea = Activation energy R = molar gas constant
T = temperature in Kelvin
Taking log on both sides

4
 Ea Ea
2.303 log K = 2.303logA - or log K = log A -
RT 2.303RT
If the values of rate constants at temp T 1 and T2 are K1 and K2.
K Ea T2 T1
log 2 =
K1 2.303R T1 T2

This equation is equation of straight line so if we plot log verses 1/T we get a
straight line.
Ea
The slope of line =
2.303R

MCQ with only one answers 2SO2 + O2 --> 2SO3

is 100 kg min-1 Hence, rate of disappearance of SO2
1. Rate constant of a reaction with a virus is 3.3x 10-4 will be:
s-1.Time required for the virus to become 75% (a) l00 kgmin-1 (b) 80 kg min-1
-1
inactivated is: (c) 64 kg min (d) 32 kg min-1
(a) 35 min (b) 70min 7. Rate constant k =1.2 x 10 mol-1 Ls-1
3

(c) 105mm (d) 17.5 min. and Ea =2.0x 10- kJmol-1 . When T
2. If in the fermentation of sugar in an enzymatic (a) A = 2.0x 102 kJmol-1
solution that is 0.12 M, the concentration of the (b) A = l.2x 103 mol-1 Ls-1
sugar is reduced to 0.06 M in 10 h and to 0.03 M in (c) A = 1.2x 103 mol-1 L-1s-1
20 h. What is the order of the reaction? (d) A = 2.4x 103 kJmol-1 s-1
(a) 1 (b) 2 (c) 3 (d) 0 8. The rate of a chemical reaction generally increases
3. For the reaction rapidly even for small temperature increase because
2NO+Br2 > 2NOBr, of rapid increase in the
the following mechanism has been given (a) collision frequency |
NO Br2 NOBr2
fast (b) fraction of molecules with energies in excess of
the activation energy'
NO NOBr2 2 NOBr
slow
(c) activation energy
Hence, rate law is: (d) average kinetic energy of molecules
(a) k NO2 Br2 (b) k NO Br2 9. Rate constant of a reaction is 0.0693 min-1. Starting
with 10 mole, rate of the reaction after 10 min is:
(c) k NOBr NO (d) k NOBr2 2 (a) 0.693 mol min-1
4. At a certain temperature, the first-order rate (b) 0.06932 mol min-1
constant k1 is found to be smaller than the second- (c) 0.0693 5 mol min-1
order rate constant k2 . If the Ea (l) of the first order (d) 0.0693 (5)2molmin-1
reaction is greater than Ea (2) of the second-order
reaction, then as temperature is raised: 10. The reaction H2(g)+2ICl(g)> I2(g)+ 2HCl(g)
(a) k2 will increase faster than k1 has a second-order rate law, rate = k[H2 ] [ICI].
(b) k1 will increase faster than k2 but will always Hence, rate-determining step is:
remain less than k2 (a) H2(g)+ICl(g)> HCl(g)+ HI(g)
(c) k1 will increase faster than k2 and become equal (b) HI(g)+ICl(g)> HCl(g)+ I2(g)
to k2| (c) both (a) and (b)
(d) k1 will increase faster than k2 and become (d) none of these
greater than k2 11. For the reaction:
5. A > B, H =-10kJmol-1, Ea=50 kJ mol-1 then A2 +2B > 2AB
Ea of B > A will be:
(a) 40 kJ mol-1 (b) 50 kJ mol-1 A 2 B dA 2
-1
(c) -50 kJ mol (d) 60 kJ mol-1 dt
6. Rate of formation of S03 in the following reaction 0.1 M 0.2 M 1x 10-2 Ms-1
5
 0.2 M 0.2 M 2 x l0-2 Ms-1 NO2 + CO NO + CO2
0.2 M 0.4M 8 x l0-2 Ms-1 Step I NO2 + NO2 k NO3 +NO
1 , slow

Order of reaction w. r. t. A2 and B are respectively; Step II NO3 + CO NO2 + CO2

k 2 , fast

(a) 1, 2 (b) 2, 1 dx
Hence, for the given reaction is:
(c) 1, 1 (d) 2, 2 dt
12. A > B kA =1015 e-2000/T (a) k1[NO2 ]2 k2[NO3] [CO]
C > D kC =1014 e-1000/T (b) k1[NO2 ]2 + k2[NO3] [CO]
Temperature T/K at which (kA = kC ) is; (c) k1[NO2]2
(a) 1000K (b) 2000 K (d) k1[NO2] + k2[CO]
2000 1000 18. For the following reaction
(c) K (d) K
2.303 2.303 A B + l0 kcaI
increase in temperature:
(a) increases rate of the forward as well as
backward reaction
13. (b) increases rate of the forward reaction but
Half-life is independent of concentration of A. decreases that of backward reaction
After 10 minutes volume of N2 gas is 10 L and after (c) decreases rate of the forward reaction but
complete reaction 50 L. Hence rate constant is : increases that of the backward reaction
2.303 2.303 (d) decreases rate of forward as well as backward
(a) log 5 min 1 (b) log 1.25 min 1
10 10 reaction.
19. for the second order reaction:
2A Product
2.303 2.303
(c) log 2 min 1 (d) log 4 min 1 the initial concentration of A is 0.1 M and rate
10 10 constant is 2x 10-3 dm3 mol-1 s-1. The half-life
14. 2N2O5 > 4NO2 + O2 period of the reaction is:
N 2 O5 NO2
If k1 N 2 O5 , k 2 N 2 O5 , (a) 5 sec (b) 50 sec
t t (c) 500 sec (d) 5000 sec
O2 20. The activation energy of a reaction is zero. At 280
k 3 N 2 O5 K rate constant is 1.6 10-6 s -1. The rate constant at
t
300 K is
then: (a) zero (b) 3.2 l0-6s-l
(a) k1 = k2 = k3 (b) 2 k1 = k2 = 4k3 -5 -1
(c) l.6 l0 s (d) 1.6 l0-6s-1
(c) 2k1 = 4k2 = k3 (d) none of these
21. For the reaction
2H2 (g) + 2NO (g) N2 (g) + 2H2O (g)
15. The rate law for the dimerisation of NO2 into N2O4 rate law is: rate = k[NO]2 [H2O2 ], Mechanism is
is given by:
d NO2
k NO2 2 Step I: 2NO N2O2
dt Step II: N2O2 + H2 > N2O + H2O
Step III: N2O + H2 N2 + H2O
Which of the following changes will change the
Rate law is true if:
value of the specific rate constant k7?
(a) step I is the slow step
(a) doubling the total pressure
(b) step II is the slow step
(b) decreasing the pressure
(c) step III is the slow step
(c) changing the volume of the flask
(d) steps I and II are slow steps
(d) changing the temperature
22. Rate constant k of a reaction is dependent on
16. When temperature of a reaction is changed from T1
temperature:
and T2 half-life is found to decrease. Thus:
K = Ae-Ea/RT
(a) T1 > T2 and reaction is endothermic
k has the least value at:
(b) T2 > T1 and reaction is exothermic
(a) high T and high Ea
(c) T1 > T2 and reaction is exothermic
(b) high T and small Ea
(d) T2 > T1 and reaction can be exothermic or
(c) low T and low Ea
endothermic
(d) low T and high Ea
17. Following reaction takes place by mechanism
6
23. Which of the these factors affect the value of the
specific rate constant for the reaction?
2A (g) B (g)
(a) temperature only
(b) temperature and concentration
(c) pressure only
(d) pressure and concentration
24. The radioisotope N-13, which has a half-life of 10
minutes, is used to image organs in the body. If the
injected sample has an activity of 40 Ci
The enthalpy change and activation energy for the
(microcurie), what is the activity after 30 minutes? reverse) reaction C + D > A + B are
(a) 10 Ci (b) 20 Ci respectively:
(c) 5 Ci (d) 2.5 Ci (a) x, y (b) x, x + y
25. A particular reaction increases by a factor of 2 (c) y, x + y (d) y, y + z
when the temperature is increased from 27C to 30. The rate of a first order reaction is 1.5x 10 2 mol l1
37C. Hence activation energy of the reaction is min1 at 0.5 M conc. of reactants. the half life of
(a) 12.9 kcal (b) 0.14 kcal the reaction
(c) 1.1 kcal (d) none is correct (a) 23.1 min (b) 8.73 min
26. What function of [X], plotted against time, will give (c) 7.53 min (d) 0.383 min
a 31. In a first order reaction conc. of reactants decreases
straight line for a second-order reaction? from 0.8 M to 0.4 M in 15 minutes . Time taken
(a) [X] (b) [X]2 for the conc. to change from 0.1 M to 0.025 M is
1 (a) 30 min (b) 60 min
(c) log[X] (d) (c) 7.5 min (d) 15 min
[X} 32. The rate equation for the reaction 2A + B
27. Two reaction with different activation energies C is found to be rate = k[A][B]. The correct
have the same rate at room temperature. Which statement in relation to this reaction is that the
statement correctly describes the rates of these two (a)the unit of k be s1
reactions at the same higher temperature? (b) value of k is independent of initial conc of A
(a) the reaction with the greater activation energy and B
will be faster (c)rate of formation of C is twice the rate of
(b) the reaction will the smaller activation energy disappearance of A
will be faster 1
(d) t 2 is constant
(c) the two reactions will have the same rate
33. The temperature dependence of rate constant (k) of
(d) temperature range is also required a chemical reaction is written in terms of
Arrhenius equation, k = A. e-Ea / RT . Activation
28. The rates of many chemical reactions double for a
energy (Ea)of the reaction can he calculated by
ten degree rise in temperature. Which of these
ploting :
factors does not contribute to this change in the rate
with increaser temperature? 1
(a) log k vs (b) k vs T
(a) the average kinetic energy of the reactant log T
species 1 1
(b) the number of collisions in a given time (c) k vs (d) log k vs
log T T
(c) the number of very eneretic spector
(d) the activation energy
34. The rate of reaction is equal to the rate constant .
29. Given the following diagram for the reaction
the order of reaction is
A+B > C+D
(a) 3 (b) 0 (c) 1 (d) 2
35. The activation energy for a simple chemical
reaction A B Ea in forward direction. The
activation energy for reverse reaction is
(a) Always double of Ea
(b) is negative of Ea
(c) is always less than Ea
(d) Can be less that or more than Ea
7
36. The reaction A B follows first order kinetics. the NO (g) + Br2(g) NOBr2(g)
time taken for 0.8 mole of A to produce 0.6 moles
of B is one hour. What is the time taken for the NOBr2 (g) + NO (g) 2NOBr(g)
conversion of 0.9 mole of A to produce 0.675 If second step is rate determining step , the order of
mole of B ? reaction with respect to NO (g) is
(a) 2 hr (b) 1 hr (a) 3 (b) 2 (c) 1 (d) 0
(c) 0.5 hr (d) 0.25 hr 43. For the reaction 2A + B 3C + D Which of the
37. For the reaction system following doesnot express the reaction rate
2NO(g) + O2(g) 2NO2 (g) ,the volume is
d ( D) dA
suddenly reduced to half its value by increasing the (a) (b)
pressure . If the reaction is of first order w.r.t. O 2 dt 2dt
and 2nd order w.r.t. NO. the rate of reaction will dC d[B]
(c) (d)
(a) diminishes to of its value 3dt dt
(b) diminishes to 1/8 of its value 44. A reaction involving two different reactants can
(c) increases to 8 times of its initial value never be
(d) increase to 4 times of its initial value (a) 2nd order (b) Bimolecular
38. In respect of equation k = A. e-Ea / RT in chemical (c) Unimolecular (d) first order
kinetics which of the following statement is 45. Consider the reaction
correct? N2 (g) + 3H2(g) 2NH3 (g)
(a) k is equilibrium constant d[ NH 3 ] d[H 2 ]
(b) A is adsorption factor the rection between and
(c) Ea energy of activation dt dt
(d) R is Rydbergs constant d[ NH 3 ] 3 d[H 2 ]
39. Select the law that corresponds to data shown ofr (a) + =
dt 2 dt
the following reaction
d[ NH 3 ] d[H 2 ]
A + B C, (b) =
Exp. [A]0 [B]0 Initial rate dt dt
1 0.012 0.035 0.10 d[ NH 3 ] 1 d[H 2 ]
2 0.024 0.070 0.80 (c) =
3 0.024 0.035 0.10
dt 3 dt
4 0.012 0.070 0.80 d[ NH 3 ] 2 d[H 2 ]
(d) =
The rate law corresponds lo the above data is: dt 3 dt
(a) rate = k[B]3 (b) rate = k[B]4 46. Rate of reaction between two reactants decreases by
3
(c) rate = k[A][B] (d) rate = [A]2[B]2 a factor of 4 if conc. of B is doubled . the order of
40. A reaction was found to be of 2nd order with reaction with respect to reactant B is :-
respect to the conc. of carbon monoxide. If conc. (a) 2 (b) 1 (c) 1 (d) 2
of carnon monoxide is doubled with everything 47. For a first order reaction
else kept the same , the rate of reaction will A B the reaction rate at a conc of 0.01 m is
(a) decrease by a factor of 4 found to be 2.0 x 105 moll1s1 . the half life
(b) double period of reaction is :-
(a) 300 s (b) 30 s
(c) remains unchanged (c) 220 s (d) 347 s
(d) Triple
41. Rate of reaction can be expressed by Arrhenius
equation k = A. e-Ea / RT . In the reaction e 48. Rate constant of a chemical reaction has unit L
represents mol1 s1 order of reaction is :
(a) total energy of reacting molecules at a temp T. (a) 0 (b) 1 (c) 2 (d) 3
(b)fraction of molecule with energy greater than 49. For a reaction xA yP [A] = 2.2 mM
activation energy of reactants . rate was found to be 2.4 mMs1 on reducing the
(c) Energy above which all the colliding molecules conc of A to half . the rate changes to 0.6 m M s 1
will react . Order of reaction is :-
(d) Energy below which colliding molecules will (a) 1.5 (b) 2.0
not react (c) 2.5 (d) 3.0
42. The following mechanism has been proposed for 50. Consider a reaction aG + bH Products
the of NO with Br2 to form NOBr

8
When concentration of both reactants G and H is
doubled, the rate increases by 8 tomes. However
when the conc. of G is doubled keeping the conc. of
H fixed . the rate is doubled. Over all order of
reaction is
(a) 0 (b) 1 (c) 2 (d) 3

9
Chemical Bonding 1

CHEMICAL BONDING

Chemical Bond : The attraction between two atoms or ions is called a chemical bond. Chemical bond
is formed either due to sharing or transfer of electrons between atoms.
A chemical bond is formed by an atom inorder to get stability by lowering its potential energy.
Atoms (noble gases) with octet configuration in outer shell are stable. Hence every atom tries to get
octet configuration either by losing or gaining or sharing electrons.

Types of chemical bond :

1) Ionic bond
2) Covalent bond
3) Metallic bond

1) Ionic bond :The electrostatic force of attraction between two oppositely charged ions is called ionic
bond.
* An ionic bond is formed due to transfer of electrons from one atom to another.
* The atom which loses electrons will form a cation and the atom which gains electrons will form an
anion. These oppositely charged ions come closer to each other due to electrostatic force of attraction
and thus form an ionic bond.
* An ionic bond is formed between two atoms when their electronegativity difference is greater
than 1.7.
* Usually an ionic bond is formed between a metal and a nonmetal.
E.g., NaCl, LiF, MgCl2 etc.,

2) Covalent Bond : The attraction between two atoms formed due to the sharing of electron pair(s) is
called covalent bond.
* It is formed when electronegativity difference between two atoms is less than 1.7.
* Usually two nonmetals form a covalent bond.
E.g., H2, F2, HCl, H2O etc.,

3) Metallic bond: It is the attraction between metal atoms in a metallic crystal. It is formed between
electropositive metal atoms.

KOSSELL AND LEWI'S ELECTRONIC THEORY OF CHEMICAL BONDING

* The atoms of inert gases are stable due to octet configuration (ns2np6) in the outer shell. Hence atoms
must posses eight electrons in their outer shell to get stability. This is referred to as octet rule.
* Helium is also highly stable due to 1s2 configuration.
* Hence every atom tries to get nearest inert gas configuration either by losing or gaining or sharing
electrons.
* Only the electrons in outer shell participate in bond formation. These electrons are called valence
electrons.
The electrons in the inner shell are called core electrons and do not participate in bond formation.
* An ionic bond is formed due to transfer of electrons between atoms whereas a covalent bond is
formed due to sharing of valence electrons.

Electrovalency: The number of valence electrons either lost or gained by an atom during the ionic
Chemical Bonding 2
bond formation is called electrovalency.

IONIC BOND FORMATION

1) LiF (Lithium fluoride)

In the formation of Lithium fluoride, Li loses one electron to get nearest inert gas - Helium's con-
figuration. Fluorine atom gains one electron to get nearest inert gas - Neon's configuration. Thus formed
Li+ and F- ions form the ionic compound LiF.
1) Li
Li + + 1e-

z=3
He 2s1 He

2) F + 1e -
F-
z=9
He 2s 2 2p5 He 2s2 2p6

3) Li F
LiF

* The electrovalencies of Li and F are equal to one.

2) MgCl2 (Magnesium chloride)

Magnesium loses two electrons to get Neon's configuration. Chlorine atom gains one electron to
get Argon's configuration. Thus formed Mg2+ and Cl- ions combine together by forming MgCl2.
1)
Mg Mg 2+ + 2e-
z=12
Ne 3s 2 Ne

2) 2 x ( Cl + 1e -
Cl- )
z=17
Ne 3s 2 3p5 Ne 3s2 3p6

3) Mg 2+ 2Cl
MgCl2

* The electrovalency of Mg is 2 and that of Cl is 1

3) AlF3 (Aluminium Fluoride)
Aluminium loses 3 electrons and Fluorine atom gains 1 electron to get Neon's configuration. The
formed Al3+ and F- ions are combined to form AlF3.
Al
Al3+ + 3e-
z=13
3s2 3p1
Ne Ne
Chemical Bonding 3

2) 3 x( F + 1e -
F- )
z=9
2s 2 2p5
He He 2s2 2p6

3) Al3+ + 3F -
AlF3

* The electrovalency of Al is 3 and that of F is 1.

4) Na2O (Sodium monoxide)
Sodium loses 1 electron and oxygen gains 2 electrons to get nearest inert gas Neon's configuration.
Thus formed Na+ and O2- ions combine to give Na2O.
1)
2x Na Na + + 1e
z=11
1s 2 2s2 2p 6 3s1 1s2 2s 2 2p 6

2)
O + 2e
O 2
z 8
1s 2 2s 2 2p 4 1s 2 2s 2 2p 6

3) 2Na + + O 2-
Na 2O

* The electrovalency of 'Na' is 1 and that of 'O' is 2.

FACTORS FAVOURING THE FORMATION OF IONIC BOND

Ionic bond is electrostatic force of attraction between cation and anion. Hence factors
favouring their formation also favour the formation of ionic bond.

Factors favouring the formation of cation :

Big atomic size : In bigger atoms, the nuclear attraction over the outer electrons is less. Hence they
lose the electrons easily to form cations.
E.g. The ease of formation of cation increases from Li+ to Cs+ in IA group with increase in size.
2) Low ionization energy : The removal of electrons is easy from atoms with low ionization energy
values. Hence these atoms form cation easily.
E.g. IA and IIA group elements readily form cations due to low ionization energies.
3) Low charge on cation : As the successive ionization energies are increased, the formation of
cations becomes difficult with increase in charge on them.
E.g. Among Na+, Mg+2 and Al+3 , the order of ease of formation is as follows
Na+ > Mg+2 > Al+3
i.e., Na is formed more readily than Mg+2 and Al+3
+

4) Octet electronic configuration : The cations with 8 electrons in the outer shell (octet configura-
tion) are highly stable and hence formed readily. Whereas cations with 18 electrons in outer shell
(Pseudo inert gas configuration) are comparatively less stable and hence are not formed easily.
Chemical Bonding 4

E.g. Ca2+ 1s 2 2s 2 2p 6 3s 2 3p 6 with octet configuration is formed easily.

8
Zn2+ 1s 2 2s 2 2p 6 3s 2 3p6 3d10 with pseudo inert gas configuration cannot be formed
18
easily.

Factors favouring the formation of anion

1) Small atomic size : Atoms with small atomic size have stronger attraction towards electron and
hence can form anions readily.
2) High electron affinity and electronegativity : The atoms, with high electron affinity and elec-
tronegativity, gain electrons easily and hence form anions readily.
E.g., Halogens can form anions readily due to small size, high electron affinity and high electronega-
tivity.
3) Low charge on anion : The formation of highly charged anions is difficult as the addition of succes-
sive electrons to the atoms becomes difficult due to repulsion from electrons in the atom. Hence anion
with low charge is formed readily.
E.g., Among C4-, N3-, O2- and F- ions, the anion with low charge (F-) is formed readily whereas the
formation of anion with higher charge (C4-) is difficult.
i.e., The order of ease of formation is C4- < N3- < O2- < F-

FAJAN'S RULES
These rules are used to predict the nature of the bond formed by atoms based on their polarizing
power and polarizability.
1) Greater the size of cation, greater is the ionic nature.
E.g. In IA group elements ionic nature increases with increase in the size of cation from Li+ - Cs+.
i.e, Increasing order of ionic nature : Li+ < Na+ < K+ < Rb+ < Cs+
less more
ionic ionic
2) Greater the size of anion, greater is the covalent nature.
E.g. Among the halides of the calcium the covalent nature increases from CaF2 to CaI2 with in-
crease in the size of anion.
Increasing order of covalent nature : CaF2 < CaCl2 < CaI2
3) Greater the charge on cation, greater is the covalent nature.
E.g. In case of Na+, Mg+2 and Al+3 , the covalent nature of cations increases with increase in the
charge as follows.
Na+ < Mg+2 < Al+3
i.e., The compounds of Al3+ are more covalent.
4) The cations with octet configuration in the valence shell exhibit more ionic nature whereas cation with
pseudo inert gas configuration exhibit more covalent nature in their compounds.
E.g. CaCl2 is more ionic [ Ca2+ has octet configuration]
Whereas CuCl, AgCl, ZnCl2 are more covalent. [ Cu+, Ag+, Zn2+ have Psuedo inert gas configu-
ration].

CRYSTAL LATTICE ENERGY (U)

The amount of energy liberated when one mole of the crystalline substance is formed from
the gaseous ions is called lattice energy (U) of the crystal.

ENERGY CHANGES IN IONIC BOND FORMATION

Chemical Bonding 5
The crystal lattice energy of an ionic crystal can be calculated by using Born-Haber cycle. For
example the lattice energy of NaCl can be calculated as follows:

BORN-HABER CYCLE : The principle involved in Born-Haber cylcle is Hess's law of constant
heat summation which can be stated as follows.

Hess's Law : The total energy change in a reaction remains same whether the reaction takes
place in one step or in several steps.

Calculation of lattice energy of NaCl

NaCl can be obtained from sodium metal and chlorine gas either in one step or in several steps as
shown below.

Direct step : NaCl crystals are formed by combining Na metal with chlorine gas in one step. The
energy evolved during this reaction is called heat of formation
Hf .
1
Na s Cl2 g
NaCls ; H f = -410.5 kJ/mol
2

Indirect method : The formation of NaCl crystals may occur in several steps as follows.
i) Sublimation of sodium : Solid sodium is first converted gaseous sodium by absorbing 108.7 kJ/
mole of energy. This is called sublimation energy H s or + S .

Na s
Na g ; Hs = + S = +108.7 kJ/mol
ii) Ionization of sodium : Gaseous sodium atoms are ionized by absorbing 492.82 kJ / mole of
energy. It is called ionization energy H i or + I .
Na +g + 1e-
Na g ; H i = + I = + 492.82 kJ/mol
iii) Dissociation of chlorine molecule : One mole of gaseous chlorine molecules are dissociated into
two moles of chlorine atoms by absorbing energy equal to 239.1 kJ/mole. This is called dissociation
energy H d or D .

Cl 2g
2Cl g ; H d = +D = 239.1 kJ/mol
But the energy required to get one mole of chlorine atoms is equal to
+D 139.2
= = +119.55 kJ/mol
2 2
1 1 +D
Cl 2 g
Cl g ; H d = = +119.55 kJ/mol
2 2 2
Chloride ion formation : The gaseous chlorine atoms are added with electrons to get gaseous chlo-
ride ions. The energy liberated in this process is called electron affinity (H e or E) .
Cl 2 g + e-
Cl-g ; H e = - E = -361.6 kJ/mol
Formation of NaCl Crystals : The gaseous Na+ and Cl- ions unite to form one mole of NaCl crys-
tals. The energy liberated during this process is called lattice energy H u or -U . This value can be
calculated by using Hess's law as follows.
Na +g + Cl- g
NaCl s ; H u = -U
Chemical Bonding 6
According to Hess's law the energy change in the steps involved in indirect method.
1
i.e. H f H s H f H d H e H u
2
(or)
D
H f S I E U
2
H d
i.e., U H f H S H i H e
2
U 410.5 108.7 492.82 119.55 (361.6) 769.97 kJ .mol 1

1 Hf
Na(s) + /2Cl2(g) NaCl(s)
H d
Hs= +S
2

Na(g) Cl(g)
-U
Hi= +I He= +E

+ -
Na (g) + Cl (g)

Born-Haber cycle

BORN LANDE EQUATION

The lattice energy of an ionic crystal is equal to the sum of attractive and repulsive forces in the crystal.
It can be calculated by using Born Lande equation as follows:

AZ .Z Be 2
U N o No n
r r
attractive repulsive
force force
Where A = Madelung constant (which depends on geometry of the crystal)
AZ .Z e 2 r n 1
B = Repulsion coefficient
n
(This depends on the structure and approximately proportional to the number of nearest
neighbours)
No = Avogadro's number
Z+ & Z- = Charges on the positive and negative ions respectively.
e = Charge of an electron.
r = Distance between the oppositely charged ions
n = Born exponent (a constant which is usually taken as 9)

Born Lande equation can be written as follows

Chemical Bonding 7

AZ .Z e 2 N o 1
U 1 n
ro

CRYSTAL STRUCTURES
Unit cell : The smallest part of the crystal which produces entire crystal upon repeating three dimen-
sionally is called unit cell.

Coordination number : Maximum number of nearest oppositely charged ions surrounding any par-
ticular ion in ionic crystal is called the coordination number of that ion.

r
Limiting radius ratio ( ): The ratio of radius of positive ion to that of negative ion is called limiting
r
radius ratio.

The coordination number and crystal structure of an ionic crystal can be predicted from the limiting
radius ratio value.

r
Limiting radius ratio ( Coordination
r ) number
Structure

less than 0.155 2 linear

0.155 - 0.225 3 Planar triangle
0.225 - 0.414 4 Tetrahedral
0.4142 - 0.732 4 Squared planer
0.4142 - 0.732 6 Octahedral
0.732 - 0.999 8 Body centered cubic

1) Crystal structure of Cesium chloride

rCs
* Limiting radius ratio ( )= 0.93.
rCl
* The coordination number is equal to 8.
* Crystal structure is body centered cubic (bcc).
* Each unit cell contains 1 Cs+ and 1 Cl- ions.
Chemical Bonding 8

Cl- Cl-

There are eight Cl- ions at the corners

Cl- Cl -
each of which contributes only 1/8th
part and one Cs+ at the centre. Hence

Cs+ 1
Number of Cl- ions = 8 x =1
8
Cl- Cl- Number of Cs+ ions = 1

Cl- Cl-

2) Crystal structure of sodium chloride

rNa
* Limiting radius ratio ( )= 0.52
rCl
* The coordination number is equal to 6.
* The crystal structure is face centered cubic (fcc).
* Each unit cell contains 4 Na+ and 4 Cl- ions.

Cl- Na+ Cl-

1
Na+ Cl- Na+ Number of Cl- ions at corners = 8 x =1
8
Cl- Na+ Cl- 1
Number of Cl- ions at the centre of faces = 6 x =3
2
Na+ Cl- Na+
Total number of Cl- ions = 1+3 = 4
Cl- Na+ Cl-

Na+ Cl- Na+ 1

Number of Na + ions on the edges = 12 x =3
4
Cl- Na+ Cl- Number of Na + ions at the centre = 1
Na+ Cl- Na+ Total number of Na + ions = 3+1 = 4

Cl- Na+ Cl-

Properties of ionic compounds

1) Ionic compounds contain oppositely charged ions which are strongly attracted to each other.
Hence these are hard substances with high melting and boiling points.
2) Ionic bond is direction less and the electrostatic forces of attraction are present in all directions
around an ion. Hence there is no isolated discrete molecule in the ionic crystal. Entire crystal is consid-
ered as the giant molecule.
3) In the solid state, ions cannot move freely and hence they do not conduct electricity . But in
fused state or in aqueous solutions, they exhibit electrical conductivity as the ions are free to move.
4) Ionic compounds are polar in nature and hence they are soluble in polar solvents like water.
These compounds do not dissolve in non polar solvent like benzene, carbon tetrachloride etc.,
Chemical Bonding 9
5) The reactions between ionic compounds occur very fast due to presence of separate ions.
e.g. A white precipitate of AgCl is formed instantly when aqueous solution of NaCl and AgNO3 are
mixed.
NaCl(aq) + AgNO3(aq) NaNO3(aq) + AgCl
6) Ionic compounds do not exhibit isomerism due to non directional nature of ionic bond.

Formula weight: Ionic compounds contain only ions and there are no molecules in it. Hence their
molar mass is expressed as formula weight instead of molecular weight.

COVALENT BOND FORMATION & LEWI'S DOT STRUCTURES

A covalent bond is formed by sharing of pair of electrons between two atoms.
It is formed between two atoms when their electronegativity difference is less than 1.7 . Usually a
covalent bond is formed between two nonmetals.
The formation of covalent bonds can be explained based on Lewi's dot structures. Atoms contrib-
ute their valence electrons for the bond formation and get octet or nearest inert gas configuration.
Covalency : The number of electrons contributed by the atom of an element in the formation of
covalent compound is known as covalency of that element.

Examples
1) H2 molecule
* Electronic configuration of hydrogen is 1s1.
* Each hydrogen atom contribute one electron to form a pair of electrons, which is shared in between
the two atoms. Thus a covalent bond is formed.
* Thus in H2 molecule, each hydrogen atom gets its nearest inert gas - Helium's configuration.
* Covalency of hydrogen is 1.

H. .H .
+ H H
or
H H
2) Cl2 molecule
2 2 6 2 5
* The electronic configuration of Cl is 1s 2s sp 3s 3p .
7
* In order to get the nearest inert gas- Argon's configuration, each chlorine contributes one electron for
the bond formation.
* Covalency of chlorine is 1.

.. .. .. ..
. + . Cl .
..
..

..

..

Cl
.. .. . . Cl
Cl ..
or
.. ..
..

. . Cl
..

Cl ..

3) Hydrogen chloride (HCl)

* Electronic configuration of hydrogen is 1s1.
2 2 6 2 5
* Electronic configuration of chlorine is 1s 2s sp 3s 3p .
7
* In the formation of HCl molecule, the hydrogen and chlorine atoms contribute one electron each for
Chemical Bonding 10
the bond formation. Thus both of them get their nearest inert gas configurations.

.. ..
H X . Cl

..

..
.. or H Cl
..
4) Methane (CH4)
2 2 2
* The electronic configuration of carbon is 1s 2s 2p .
4
1
* The electronic configuration of hydrogen is 1s .
* The carbon atom forms four covalent bonds by contributing four of its valence electrons for the bond
formation. It forms 4 bonds with four hydrogen atoms. Thus it gets octet configuration.
* Covalency of carbon is 4.

H H
.x
.
H x C. . x H or H C H
x
H H

5) Ammonia (NH3) :
* The electronic configuration of nitrogen is 1s2 2s 2 2p3 .
5
1
* The electronic configuration of hydrogen is 1s ,
* In the formation of Ammonia molecule, nitrogen atom contributes 3 of its electrons to form three
bond pairs which are shared with hydrogen atoms. Thus nitrogen forms 3 single bonds with three
hydrogen atoms and gets the configuration of Neon.
* Covalency of nitrogen is 3.

.. ..
H x .N. x H or H N H
.
x

H H
5) H2O molecule
* Electronic configuration of oxygen is 1s2 2s 2 2p 4 .
6
1
* Electronic configuration of Hydrogen is 1s .
* In the formation of water molecule, oxygen atom contributes two electrons to form two bond pairs
which are shared with hydrogen atoms. Thus two bonds are formed by oxygen atom to get the configu-
ration of neon. There are also two lone pairs on oxygen atom.
* Covalency of oxygen is 2.

.. ..
H .O.
x x H or H O H
.. ..
6) Oxygen molecule (O2)
2 2 4
* The electronic configuration of oxygen is 1s 2s 2p .
6
* In the formation of oxygen molecule, each oxygen atom contributes 2 electrons to form 2 bond pairs.
Chemical Bonding 11
Thus a double bond is formed between oxygen atoms. Thus each oxygen atom gets Neon's configura
tion.

.. .. .. ..
.. .
O .O
.. or O
.. O
..
7) Nitrogen molecule (N2)
* The Electronic configuration of nitrogen is 1s2 2s 2 2p3 .
5
* In the formation of Nitrogen molecule, each nitrogen atom contributes 3 electrons to form 3 bond
pairs. Thus a triple bond between nitrogen atoms is formed. Each nitrogen atom gets Neon's configura-
tion.
or
...
...
.. N N N N
..

..

..
8) Carbon dioxide (CO2)
2 2 2
* Electronic configuration of carbon is 1s 2s 2p .
4
2 2 4
* Electronic configuration of oxygen is 1s 2s 2p .
6
* In carbon dioxide, carbon atom forms double bond with each oxygen. Thus both oxygen and carbon
..
..

atoms get the octet configuration in their valence shell.

.. .. .. ..
or O C O
..

O
..

O C
..
..
..

9) Ethylene molecule (C2H4)

2 2 2
* Electronic configuration of carbon is 1s 2s 2p
4
* Electronic configuration of hydrogen is 1s1
H H H H
*. .*
.C . . C. or C C
* *
H H H H

Molecules violating octet rule:

BeCl2 (Beryllium chloride)

* Electronic configuration of Beryllium is 1s 2 2s 2
2
2 2 6 2 5
* Electronic configuration of Chlorine is 1s 2s sp 3s 3p .
7
* In the formation of Beryllium chloride, the beryllium atom contributes its two valence electrons and
forms two bond pairs. These are shared with chlorine atoms.
* BeCl2 is a stable molecule, even though beryllium gets only four electrons in its valence shell. This is
Chemical Bonding 12
the violation of octet rule.
* Covalency of beryllium is 2.

.. .. .. ..
Cl . . Cl or Cl Be Cl

..
..
Be

..
..
x x
.. .. .. ..
BCl3 (Boron trichloride)
2 2 1
* Electronic configuration of Boron is 1s 2s 2p .
3
2 2 6 2 5
* Electronic configuration of chlorine is 1s 2s sp 3s 3p .
7
* In BCl3 molecule, boron contributes 3 of its valence electrons and forms three bond pairs with
chlorine atoms. There are only six electrons in the valence shell of boron atom in BCl3. But still it is
stable. It is an electron deficient compound. It is also the violation of octet rule.
* Covalency of boron is 3.

.. ..
Cl
..
..

Cl
..
..
.
.. x .. .. ..
. . Cl or Cl
..
B Cl B
..

Cl
..
..

x x
.. .. .. ..

PCl5 (Phosphorous pentachloride)

2 2 6 2 3
* Electronic configuration of phosphorus is 1s 2s 2p 3s 3p .
5
2 2 6 2 5
* Electronic configuration of chlorine is 1s 2s sp 3s 3p .
7
In the formation of PCl5 molecule, phosphorus contributes five electrons in it's valence shell and
forms five bonds with chlorine atoms. There are 10 electrons in the valence shell of phosphorus in this
molecule. It is a stable molecule and violates octet rule.
* Covalency of phosphorus in this molecule is 5.

.. ..
Cl
..
..

.. Cl
..

..
..

. .. ..
Cl . Cl
..

x
.
..

Cl
..

.. x Cl
..

x .. or ..
P .. P
x x
. .. .. ..
.. .
Cl Cl
..
..

Cl Cl
..

..

.. .. .. ..

SF6 (Sulphur hexafluoride) :

* Electronic configuration of Sulphur is 1s 2 2s2 2p 6 3s 2 3p 4 .
6
Chemical Bonding 13

* Electronic configuration of Fluorine is 1s2 2s 2 2p5

7
* Sulphur contributes six of its valence electrons to form 6 bonds with six fluorine atoms. Thus there
are 12 electrons in the valence shell in sulphur atom.
In violates octet rule and is still stable.
* Covalency of sulphur in this molecule is 6.

F F
F * F F F
* * or
S
* *
S
F * F F F
F F

Conclusion: Lewi's electronic theory could not explain the shapes and bond angles of molecules. It
also could not explain why some molecules are stable eventhough they violate octet rule.

Some more examples:

1) H2S 2) CO32-

_ _
x x
O O
.. .. x
C xx O C O
H .S. x x H or H S H x or
.. .. Ox O
x _
Hydrogen sulphide _

Carbonate ion

3) SiCl4 4) HCOOH

.. ..
Cl O O
..
..

Cl ..
..
..

.. .x .. ..
x.
Si . x Cl Cl Si Cl H C OR H C
..

Cl
..

or
..
..

.. .x .. ................
Cl O H O H
..
..

Cl
..
..

..
..
Silicon tetrachloride Formic acid

5) NF3 6) HNO3

.. xx .. xx + +
. N . F F N F O N O H O N O H
..

F x
..

x
.. . .. or
x
` O O
F F - -
Nitrogen trifluoride Nitric acid

7) CO 8) O3
Chemical Bonding 14

:
:
::: : : O :O

: :
O:
: :
C O or C O or :

: :
:

:
:
O O
: O

:
:
Carbon monoxide molecule Ozone molecule
-1 +
8) NO2 9) NH4

+ +
- H
- H
O N O or O N O ..
H x .N. x H or H N H
.
x
Nitrite ion
H H

Formal charge (Qf)

It is the charge on an atom in a molecule assigned by assuming all the atoms have same electrone-
gativity and the electron pairs are shared equally. It is calculated as follows:
1
Qf = N A - N LP - N BP
2
Where NA = Number of electrons in the valence shell of free atom.
NLP = Number of electrons in the lone pairs (unshared pairs).
NBP = Number of electrons in the bond pairs.

Examples:
1) PH3 molecule
Lewi's dot structure:

.. ..
H x .P. x H H P H
.
x or
H H

1 6
Formal charge on 'P' = N A - N LP - N BP 5 2 0
2 2
1 2
N BP 1 0 0
Formal charge on 'H' = N A - N LP -
2 2
2) N2O molecule: It exists in following two resonance forms.
For the following first resonance form:
- + - +
:

:
:

:N N O
: or : N : :N : :O :
(1 ) (2 ) (1 ) (2 )

1 4
Formal charge on first nitrogen 'N(1) ' = N A - N LP - N BP 5 4 1
2 2
1 8
Formal charge on second nitrogen 'N(2) ' = N A - N LP - N BP 5 0 1
2 2
Chemical Bonding 15

1 4
Formal charge on 'O' = N A - N LP - N BP 6 4 0
2 2

For the following second resonance form:

+ - + -

:
:N N O
:
or :N : ::
N
:
O
:
(1 ) (2)

:
(1 ) (2 )

1 6
Formal charge on first nitrogen 'N (1)' = N A - N LP - N BP 5 2 0
2 2
1 8
Formal charge on second nitrogen 'N (2) ' = N A - N LP - N BP 5 0 1
2 2
1 2
Formal charge on 'O' = N A - N LP - N BP 6 6 1
2 2
Hence the formal charges vary with structural environment.

VALENCE SHELL ELECTRON PAIR REPULSION (VSEPR) THEORY

* Following are the important postulates of VSEPR's theory proposed by Nyholm, Gillespie.
1) The shape of a molecule can be determined from the arrangement and repulsions between the
electron pairs present in the valence shell of central atom of that molecule.
2) There are two types of valence shell electron pairs viz.,
i) Bond pair and ii) Lone pair
3) The electron pairs in the valence shell the repel each other and determines the shape of the molecule.
The magnitude of the repulsion depends upon the type of electron pair.
4) The bond pair is attracted by nuclei the occupies less space and hence it causes less repulsion.
Whereas, the lone pairs are only attracted by one nucleus and hence occupy more space. As a result,
the repulsion caused by them is greater.
The order of repulsion between different types of electron pairs is as follows :
Lone pair - Lone pair > Lone Pair -Bond pair > Bond pair- Bond pair
5) When the valence shell of central atom contains only bond pairs, the molecule gets symmetrical
structure, whereas the symmetry is distorted when there are lone pairs along with bond pairs.
6) The bond angle decreases due to the presence of lone pairs.
7) The repulsion increases with increase in the number of bonds between two atoms.
E.g. Triple bond causes more repulsion then double bond which in turn causes more repulsion than
single bonds.
8) The repulsion between electron pairs increases with increase electronegativity of central atom and
hence the bond angle increases.
9) Shapes of molecules can be predicted from the number of electron pairs in the valence shell of central
atom as follows:
Chemical Bonding 16

THE GEOMETRY OF MOLECULES CONTAINING ONLY BOND PAIRS IN THE CENTRAL ATOM
Number of
Formula Molecular geometry Examples
bond pairs
2 AB2 Linear B A B BeCl2, BeF2
B
Trigonal
3 AB3 BF3, BCl3
planar A
B B

4 AB4 Tetrahedral A
B
CH4, CCl4
B
B

B
Trigonal
5 AB5 B A PCl5, PF5
bipyramidal
B
B

B B
6 AB6 Octahedral A SF6
B B

B
Chemical Bonding 17

GEOMETRY OF MOLECULES CONTAINING CONTAINING ONE OR MORE

LONE PAIRS IN CENTRAL ATOM
Total
number Number Number
Shape of
of of bond of lone Formula Bond angle Examples
molecule
electron pairs pairs
pairs
o
3 2 1 AB2E Angular 120 SO2
o
Trigonal 107 48 NH3
3 1 AB3E
Pyramidal 102o30 NF3
4
Angular 104o28 H2O
2 2 AB2E2 o
(V- shaped) 103 F2O
4 1 AB4E See-Saw SCl4 , SF4
5 3 2 AB3E2 T-Shape 90o ClF3
o -
2 3 AB2E3 Linear 180 XeF2, I3
Square o
5 1 AB5E 90 BrF5
pyramidal
6
Square o
4 2 AB4E2 90 XeF4
planar
Where A = central atom
B = atom linked to the central atom
E = Lone electron pair

Explanatory examples:
1) BeCl2: The valence shell of central atom, beryllium contains only two bond pairs. Hence it is linear
in shape with 180o bond angle.

180o
Cl Be Cl

Linear molecule
2) BF3: The valence shell of the central atom - boron contains only three bond pairs. Hence it's shape
is trigonal planar with 120o bond angle.

Cl

Cl
120o Cl

Trigonal planar shape

3) CH4: The valence shell of the central atom - carbon contains only four bond pairs. Hence it is
tetrahadral in shape with 109o28' bond angle.
The bond pairs are arranged tetrahedral symmetry so as to minimize repulsions. If the bond pairs
Chemical Bonding 18
are arranged in square plane, the angles between them will be only 90o and the repulsions will be more
than in case of tetrahedral arrangement. Hence tetrahedral structure is more favorable than square
planar structure.

109o28'
C
H
H
H
Tetrahedral structure of methane

4) NH3: There are three bond pairs and one lone pair in the central atom, nitrogen. The bond angle is
decreased from 109o28' to 107o48' due to repulsion caused by lone pair.

N
H H
107o48'
H

Trigonal pyramidal structure of ammonia molecule

5) H2O: There are two bond pairs and two lone pairs in the central atom, oxygen. The bond angle is
decreased from 109o28' to 104o28' due to repulsion caused by two lone pairs.

O
H
o
104 28'
H
Angular shape of water molecule

VALENCE BOND THEORY (VBT)

This theory was proposed by Heitler and London to explain the formation of covalent bond. The
main postulates are as follows:
* A covalent bond is formed by the overlapping of two half filled atomic orbitals containing electrons
with opposite spins.
* Thus formed electron pair is shared between two atoms.
* The electron density along the internuclear axis between two bonded atoms increases due to over-
lapping. This confers stability to the molecule.
* Greater the extent of overlapping, stronger is the bond formed. The direction of the covalent bond is
decided by the direction of overlapping.
* There are two types of covalent bonds based on the pattern of overlapping as follows:
(i) bond:- The covalent bond formed due to overlapping of atomic orbital along the inter nucleus
axis is called bond.
It is a stronger bond with cylindrical symmetry.
(ii) bond :- The covalent bond formed by sidewise overlapping of atomic orbitals is called -
Chemical Bonding 19
bond.
In this bond, the electron clouds are present above and below the internuclear axis. It is a weaker
bond.

Note: The 's' orbitals can only form bonds, whereas the p, d & f orbitals can form both and
bonds.

Examples
1) H2 molecule
* Electronic configuration of hydrogen is 1s1.
* In the formation of hydrogen molecule, two half filled 1s orbitals of hydrogen atoms overlap along the
internuclear axis and thus form a s-s bond.

H + H H H

1s orbital 1s orbital s s bond

2) Cl 2 molecule
* Electronic configuration of Cl is 1s2 2s2 2p6 3s2 3px2 3py2 3pz1
* The two half filled 3pz atomic orbitals of two chlorine atoms overlap along the internuclear axis and
thus by forming a p-p bond.

Cl + Cl Cl Cl

3pz orbital 3pz orbital p p bond

3) HCl molecule
* Electronic configuration of hydrogen is 1s1.
* Electronic configuration of Cl is 1s2 2s2 2p6 3s2 3px2 3py2 3pz1
* The half filled 1s orbital of hydrogen overlap with the half filled 3pz atomic orbital of chlorine atom
along the internuclear axis to form a s p bond.

H + Cl H Cl

1s orbital 3pz orbital s p bond

4) O2 molecule
* Electronic configuration of O is 1s2 2s2 2px2 2py1 2pz1
* The half filled 2px orbitals of two oxygen atoms overlap along the internuclear axis and form
p-p bond. The remaining half filled 2pz orbitals overlap laterally to form a p-p bond. Thus a double
bond (one and one ) is formed between two oxygen atoms.

p p bond

p p bond
O + O O O

5) N2 molecule
* Electronic configuration of N is1s2 2s2 2px1 2py1 2pz1
* p-pbond is formed between two nitrogen atoms due to overlapping of half filled 2px atomic
Chemical Bonding 20
orbitals axially. The remaining half filled 2py and 2pz orbitals form two p-p bonds due to lateral
overlapping. Thus a triple bond (one and two )is formed between two nitrogen atoms.
p p

p p

p p

N N

Valence bond theory could not explain the structures and bond angles of molecules with more than
three atoms. E.g. It could not explain the structures and bond angles of H2O, NH3 etc.,

Inorder to explain the structures and bond angles of molecules, Linus Pauling modified the valence
bond theory by proposing hybridization concept.

HYBRIDIZATION
The intermixing of atomic orbitals of almost equal energies of an atom to give an equal
number of identical and degenerate hybrid orbitals is called hybridization.

Characteristics of hybridization :
1) Pure atomic orbitals of same atom should participate in the hybridization.
2) The energies of atomic orbitals participating in hybridization must be nearly same.
3) The number of hybrid orbitals formed is equal to the number of atomic orbitals participating in the
hybridization.
4) The hybrid orbitals formed are identical in shape and degenerate.
5) These hybrid orbitals are symmetrically arranged around the nucleus so as to minimize the repulsion
between them and thus get maximum stability.
6) The filling of electrons into hybrid orbitals follows Pauli's exclusion principle and Hund's rule of
maximum multiplicity.
7) A hybrid orbital may be empty or half-filled or full filled.
8) Usually hybrid orbitals form sigma bonds only.

TYPES OF HYBRIDIZATION

1) 'sp' hybridization
* Intermixing of one 's' and one 'p' orbitals of almost equal energy to give two identical and degen-
erate hybrid orbitals is called 'sp' hybridization.
* These sp-hybrid orbitals are arranged linearly at 180o of angle.
* They possess 50% 's' and 50% 'p' character.

s orbital p orbital sp hybrid orbitals

Examples:
1) BeCl2
* Electronic configuration of 'Be' in ground state is 1s2 2s2
Chemical Bonding 21

* Electronic configuration of 'Be' in excited state is 1s 2 2s1 2p1x

2s 2px 2py 2pz

sp
hybridization
(2 bonds)
* In the excited state, beryllium undergoes 'sp' hybridization by using a 2s and a 2p orbitals. Thus two
half filled 'sp' hybrid orbitals are formed. These are arranged linearly.
* These half filled sp-orbitals form two sp p bonds with two 'Cl' atoms.
* Thus BeCl2 is linear in shape with the bond angle of 180o.

sp p sp p
Cl Be Cl
BeCl2
Hybridization - sp
180o Shape - linear
Cl Be Cl Bond angle - 180o
Linear molecule

2) Acetylene (C2H2)
* Electronic configuration of 'C' in ground state is 1s2 2s2 2p2
* Electronic configuration at 'C' in excited state is 1s2 2s1 2p3

2s 2px 2py 2pz

sp
hybridization
(2 bonds) pure
orbitals
form
2 bonds

* Each carbon atom undergoes 'sp' hybridization by using one 2s and one 2p orbitals in the excited
state. Thus two half filled 'sp' orbitals are formed. These are arranged linearly.
The two carbon atoms form one sp sp bond with each other by using sp-orbitals. They also form
two p p bonds by overlapping half filled pure p-orbitals ( 2py and 2pz). Thus a triple bond (1 & 2 )
is formed between carbon atoms.
Each carbon also forms a sp s bond with the hydrogen atom.
Thus acetylene molecule is linear with 180o bond angle.
Chemical Bonding 22

p p
p p
sp s sp sp
H C C H
C2 H 2 - Acetylene
Hybridization - sp
Shape - linear
180o
Bond angle - 180o
H C C H

Linear structure of acetylene molecule

sp2 hybridization :
* Intermixing of one 's' and two 'p' orbitals of almost equal energy to give three identical and degener-
ate hybrid orbitals is known as sp2 hybridization.
* The three sp2 hybrid orbitals are oriented in trigonal planar symmetry at angles of 1200 to each other.
* sp2 hybrid orbitals have 33.3% 's' character and 66.6% 'p' character.

+ +

s orbital px orbital py orbital sp2 hybrid orbitals

Examples:
1) BCl3
* Electronic configuration of 'B' in ground state is 1s2 2s2 2p1
* Electronic configuration of 'B' in excited state is 1s2 2s12px12py1

2s 2px 2py 2pz

sp2
hybridization
(3 bonds)
In the excited state, Boron undergoes sp2 hybridization by using a 2s and two 2p orbitals. Thus
three half filled sp2 hybrid orbitals which are oriented in trigonal planar symmetry are obtained.
Boron forms three sp2 -p bonds by using sp2 hybrid orbitals with three chlorine atoms. Each
chlorine atom uses it's half filled p-orbital for the bond formation.
Thus the shape of BCl3 is trigonal planar with Cl-B-Cl bond angles equal to 120o.
Chemical Bonding 23

Cl
Cl

B
B
Cl
120o Cl
Cl Cl

Trigonal planar structure of BCl3

BCl3 - Boron trichlorine

hybridization - sp 2
shape - Trigonal planar
Bond angle - 120o

2) Ethylene (C2H4).
* Electronic configuration of 'C' in ground state is 1s2 2s2 2p2
* Electronic configuration at 'C' in excited state is 1s2 2s1 2p3

2s 2px 2py 2pz

sp2
hybridization
(3 bonds)
pure
orbital
forms
one bond

* In the excited state, each carbon in ethylene undergoes sp2 hybridization by mixing 2s and two 2p
orbitals. Thus three half filled sp2 hybrid orbitals are formed in trigonal planar symmetry. There is also a
half filled 2pz orbital on each carbon.
* The carbon atoms form a sp2 -sp 2 bond with each other by using hybrid orbitals.

The remaining pure atomic orbitals overlap laterally and form a p-p bond.
* There is a double bond (1 & 1 ) between two carbon atoms.
* Each carbon atom also forms two sp 2 -s bonds with two hydrogen atoms.
* Thus ethylene molecule is planar with H-C-H & C-C-H bond angles equal to 120o.
* All the atoms are present in one plane.
Chemical Bonding 24

p p
H H
sp 2 sp 2 H H C2 H 2 - Ethylene
o
C C 120
C C sp 2 s Hybridization - sp 2
H H
Shape - planar
H H
Bond angle - 120o
Planar structure of ethylene molecule

sp3 hybridization:-
* Intermixing of one 's' and three 'p' orbitals of almost equal energy to give four identical and degener-
ate hybrid orbitals is called sp3 hybridization.
* Thus formed four sp3 hybrid orbitals are oriented in tetrahedral symmetry with 109028' angle with
each other.
* In these orbital the s character is 25% and p character is 75%.

+ + +

s orbital px orbital py orbital pz orbital sp3 hybrid orbitals

Examples:
Methane (CH4)
* Electronic configuration of 'C' in ground state is 1s2 2s2 2p2
* Electronic configuration at 'C' in excited state is 1s2 2s1 2p3

2s 2px 2py 2pz

sp3
hybridization
(4 bonds)

* In the excited state, the carbon atom undergoes sp3 hybridization by mixing one 2s and three 2p
orbitals. Thus four half filled sp3 hybrid orbitals are formed in tetrahedral symmetry.
* Each of these form sp3 - s bond with hydrogen atom. Thus carbon forms four bonds with four
hydrogen atoms.
* Methane molecule is tetrahedral in shape with 109028' bond angle.
Chemical Bonding 25

H H
sp3 s
109o28'
CH 4 - Methane
C C
H H Hybridization - sp3
H H Shape - Tetrahedral
H H Bond angle - 109o 28 '
Tetrahedral structure of methane

2) Ethane (C2H6)
* Electronic configuration of 'C' in ground state is 1s2 2s2 2p2
* Electronic configuration at 'C' in excited state is 1s2 2s1 2p3

2s 2px 2py 2pz

sp3
hybridization
(4 bonds)
* In the excited state, each carbon atom undergoes sp3 hybridization by using one 2s and three 2p
orbitals. Thus four half filled sp3 hybrid orbitals are formed in tetrahedral symmetry around each car-
bon.
* The two carbon atoms form a sp3 - sp3 bond with each other by overlapping sp3 hybrid orbitals
axially.
Each carbon atom also forms three sp3 -s bonds with hydrogen atoms.

* Thus there is tetrahedral symmetry around each carbon with HCH and HCC bond angles equal
to 1090 28' .

H H

sp3 sp 3 H 109o28' H
sp3 s 109o28'
C C C
C H H H
H
H H

H H
Structure of Ethane molecule

C 2 H 6 - Ethane
Hybridization - sp3
Bond angle - 109o 28 '
3) Ammonia (NH3)
* Electronic configuration of nitrogen is 1s2 2s2 2px1 2py1 2pz1
Chemical Bonding 26

2s 2px 2py 2pz

sp3
hybridization
(3 bonds)
* Nitrogen undergoes sp3 hybridization by using one 2s and three 2p orbitals. Thus formed four sp3
orbitals are arranged in tetrahedral symmetry. Among them three are half filled and one is full filled.
* Nitrogen forms 3 sp3 -s bonds with three hydrogen atoms by using three half filled hybrid orbitals.
The bond angle is decreased from 1090 28'to 1070 48' due to the repulsion caused by lone pair.
Thus ammonia acquires trigonal pyramidal shape.

N sp3 s N NH 3 - Ammonia
H H H Hybridization - sp3
H 107o48' Shape - Trigonal pyramidal
H
H Bond angle - 107o 48'
Trigonal pyramidal structure of ammonia molecule

4) H2O (Water molecule)

* Electronic configuration of oxygen is 1s2 2s2 2px2 2py1 2pz1

2s 2px 2py 2pz

sp3
hybridization
(2 bonds)
* Oxygen atom undergoes sp3 hybridization by mixing a 2s and three 2p orbitals and forms four sp3
hybrid orbitals arranged in tetrahedra symmetry. Among thenm two are half filled and the remaining two
are completely filled.
Oxygen forms two sp3 -s bonds with hydrogen atoms by using half filled hybrid orbitals.
The bond angle is decreased from 1099 28' to 1040 28' due to repulsions caused by two lone
pairs. Thus water molecule gets angular shape (V shape).

sp 3 s O water - H 2 O
O
H Hybridization - sp3
H o
104 28' shape - Angular
H
H Bond angle - 104o 28'
Angular shape of water molecule

sp3d Hybridization
* The intermixing of one 's', three 'p' and one 'd' orbitals to give five identical and degenerate hybrid
Chemical Bonding 27
3
orbitals is called sp d hybridization.
* Thus formed sp3d orbitals are arranged in trigonal bipyramidal symmetry. Among them, three are
arranged in trigonal plane and the remaining two orbitals are present perpendicularly above and below
the trigonal plane.

sp3d hybrid orbitals

Examples:
1) PCl5 (phosphorus pentachloride)
* E.configuration of 'P' in ground state is 1s2 2s2 2p6 3s2 3p3
* E.configuration of 'P' in excited state is 1s2 2s2 2p6 3s1 3p3 3d1

3s 3p 3d

sp3d
hybridization
(5 bonds)

* In the excited state, phosphorus undergoes sp3d hybridization by using a 3s, three 3p and one 3d
orbitals which are arranged in trigonal bipyramidal symmetry.
* By using these half filled sp3d orbitals, phosphorous forms five sp3d - p bonds with chlorine atoms.
Each chlorine atom makes use of half filled 3pz orbital for the bond formation.
* The shape of PCl5 molecule is trigonal bipyramidal with 1200 and 900 of Cl - P - Cl bond angles.
Cl
Cl PCl5 (Phosphorous pentachloride)
90o
Cl P 120o Hybridization - sp3d
Shape - Trigonal bipyramidal
Cl Bond angles - 120o & 90o
Cl

sp3d2 hybridization
* Intermixing of one 's', three 'p' and two 'd' orbitals of almost same energy by giving six identical and
degenerate hybrid orbitals is called sp3d2 hybridization.
* These six sp3d2 orbitals are arranged in octahedral symmetry by making 900 angles to each other.
Chemical Bonding 28

sp3d2 hybrid orbitals

Examples:
1) Sulfur hexa flouride (SF6)
* E.configuration of 'S' in ground state is 1s2 2s2 2p6 3s2 3p4
* E.configuration of 'S' in 2nd excited state is 1s2 2s2 2p6 3s1 3p3 3d2

3s 3p 3d

sp3d2
hybridization
(6 bonds)

* In the second excited state, sulfur under goes sp3d2 hyrbidization by mixing a 3s, three 3p and two 3d
orbitals. Thus formed six half filled sp3d2 hybrid orbitals are arranged in octahedral symmetry.
Sulfur atom forms six sp3d 2 - p bonds with 6 fluorine atoms by using these sp3d2 orbitals. Each
flourine uses is half-filled 2pz orbitals for the bond formation.
SF6 is octahedral in shape with F -S- F bond angles equal to 90o.

F
F F SF6 - Sulfur hexafluoride
Hybridization - sp3d 2
S
shape - Octahedral
F F Bond angle - 90o
F

Properties of covalent compounds

1) In covalent compounds, weak vander Wall's forces of attraction are present between the
molecules. Hence they have low melting and boiling points.
2) Covalent compounds do not conduct electricity because of absence of either free electrons or
ions in them.
3) Covalent compounds are mostly non polar and hence are more soluble in non polar solvents like
benzene, carbon tetrachloride etc.
But some covalent compounds are polar in nature like glucose, fructose etc., and hence are soluble
in polar solvents like water and alcohol.
4) The reactions between covalent compounds involve bond breaking and bond making. As the
bond breaking requires energy, the reactions between them occur slowly.
5) Covalent bond has specific direction. Hence these compounds exhibit isomerism.
Isomerism is the phenomenon exhibited by different compounds possessing the same
molecular formula.
e.g. Following are the isomers with the molecular formula C2H6O.
C2H5OH - Ethyl alcohol
Chemical Bonding 29
CH3-O-CH3 - Diethyl ether

COORDINATE COVALENT BOND

The covalent bond formed due to the donation of a pair of electrons by one atom to the
other is called coordinate covalent bond.

* The atom which donates the electron pair is called as donor, whereas the atom which accepts that
pair is called as acceptor.
* Both donor and acceptor will share the electron pair.
* Coordinate bond is also known as dative bond.
* It is represented by an arrow pointing towards the acceptor.

Examples:
1) Formation of Ammonium ion (NH4+)
* Ammonium ion is formed when ammonia reacts with hydrogen ion. In the formation of ammonium
ion, the sp3 orbital with a lone pair on nitrogen overlaps with the empty 1s orbital of hydrogen ion to
form a coordinate covalent bond.

H3N: + H+ [H3N H]+ (or) [NH4]+

Donor Acceptor Ammonium ion

* Ammonium ion contains 4 bond pairs in the valence shell of nitrogen atom and hence it is tetrahedral
in shape with 109o28' bond angles. The hybridization of nitrogen will remain sp3 only.

+
H

109o28'
N
H
H
H

Tetrahedral shape of NH4+

Note: In NH4Cl, there are three covalent bonds, one coordinate covalent bond and an ionic bond.
Ionic bond is present between NH4+ and Cl- ions.

2) Formation of Ammonia-boron trifluoride

* The ammonia molecule donates a lone pair of electrons on nitrogen atom to the empty 'p' orbital of
boron in BF3. Thus a coordinate bond is formed. During the bond formation, the sp3 orbital containing
the lone pair on nitrogen overlaps the empty 'p' orbital of boron.

H3N: + BF3 [H3N BF3]

Donor Acceptor

* The hybridization in boron is changed from sp2 to sp3 during the formation of coordinate covalent
bond. Hence the geometry around boron in the complex formed will be tetrahedral.
Chemical Bonding 30

H H
H H
N B

H H
3) Formation of Hydronium ion
* The sp3 orbital containing lone pair on oxygen in water molecule overlaps with the empty 1s orbital on
hydrogen ion to form a coordinate covalent bond.
:

:
H2O: + H+ [H2O H]+ or H3O+
Donor Acceptor Hydronium ion

2) Formation of [AlCl4]-
* The chloride ion (Cl-) donates a lone pair of electrons to the empty 'p' orbital of aluminium in AlCl3.
Thus a coordinate bond is formed. During the bond formation, the 'p' orbital containing the lone pair on
chloride ion overlaps the empty 'p' orbital of aluminium.

_
Cl
Cl _ :
Cl
:

Cl Al + : Cl : Al Cl :
:
:

Cl Cl

Acceptor donor AlCl4-

Planar Tetrahedral

* The hybridization in aluminium is changed from sp2 to sp3 during the formation of coordinate covalent
bond. Hence the geometry around aluminium in AlCl4- will be tetrahedral.

More examples:
SO2 and SO3 also considered to have coordinate covalent bonds according to octet rule as shown
below.
O
:

S S

O O O O

Properties of compounds containing coordinate covalent bond

Properties of compounds having coordinate covalent bond are similar to covalent compounds.
They do not conduct electricity because of absence of either free electrons or ions in them. They are
soluble mostly in non polar solvents like benzene, carbon tetrachloride etc., . But less soluble in polar
solvents like water and alcohol.
But their boiling and melting points are niether very high as in case of ionic compounds nor very
low like in case of covalent compounds.

MOLECULAR ORBITAL THEORY (MOT)

* Molecular orbital theory was proposed by Hund and Mulliken.
Chemical Bonding 31
* The important postulates of this theory are given below.
1) According to this theory, the orbitals in a molecule are different from those of atoms. The
electrons of all the bonded atoms in a molecule revolve under the influence of all the nuclei in molecular
orbitals.
2) The atomic orbitals (AO's) of the bonded atoms combine linearly to form molecular orbitals
(MO's) which are occupied by the electrons of bonded atoms.
Molecular orbital is a region around the nuclei of all the bonded atoms in a molecule where
the probability of finding electrons is maximum.
3) Only those atomic orbitals with almost same energy and symmetry with respect to internuclear
axis can combine to form molecular orbitals.
4) The number of molecular orbitals formed is numerically equal to the number of atomic orbitals
combining.
5) The shapes of molecular orbitals depend on the shapes of atomic orbitals.
6) Each molecular orbital can accommodate a maximum of only two electrons.
7) Each molecular orbital is associated with certain amount of energy and are arranged in their
increasing order of energy.
8) The degenerate molecular orbitals posses same energy and are filled with electrons according to
Hund's rule. But they may be arranged in different directions.
9) The MO's which have lower energy than AO's are called bonding orbitals, whereas those with
higher energy are known as anti bonding orbitals. The number of bonding orbitals formed is equal to
the number of anti bonding orbitals.
The orbitals which are not involved in the combination are called non bonding orbitals.
The order of energies of different types of MO's is:
Bonding orbitals < Non bonding orbitals < Anti bonding orbitals

Schematic diagram of MO's

Anti bonding orbitals

Energy AO's AO's

Non bonding orbitals

Bonding orbitals

10) The bond order of the molecule can be calculated by using the following formula.
number of bonding electrons - number of antibonding electrons
Bond order (B.O) =
2
Chemical Bonding 32

S.No Atomic orbitals Molecular orbitals

1. They belong to one specific atom only. They belong to all the atoms in a
molecule.
2. Characteristic of atoms. Formed when atomic orbitals of almost
same energy combine.
3. Simple shapes. Complex shapes.
4. Named as s, p, d, f Named as , , ....
5. Less stable than bonding and more Either more or less stable than atomic
stable than anti bonding orbitals. orbitals.

Bonding and Anti bonding orbitals

Bonding molecular orbitals are formed when the orbitals with same signs of wavefunction are
combined, whereas anti bonding molecular orbitals are formed when the orbitals with different signs of
wavefunctions are combined.
Depending on the pattern of overlapping, number of nodes and symmetry, the molecular orbitals
are again divided into two types viz., & .
-Molecular orbitals
-Molecular orbitals are formed due to linear combination of atomic orbitals along the inter-
nuclear axis of bonded atoms. They have cylindrical symmetry about the axis. Bonding orbital is
designated as , whereas antibonding orbital is designated as * .
Illustrations:
Combination of two 's' orbitals along the internuclear axis

+ + + + +
+ +

s s s
bonding orbital
Chemical Bonding 33

+ - + - + -
+
s s
s *
anti bonding
orbital

Combination of 's' and 'p' orbitals along the internuclear axis

+ + +
+ + - + -
+
-

p s p
s
bonding orbital

- -
+ + - + - - + -

p s p *
s
bonding orbital

Combination of two 'p' orbitals along the internuclear axis

+
- + + + - - ++ - -
+
-

p p p
bonding orbital

- + + - + - +- + - + - +

p p p*
anti bonding
orbital

-Molecular orbitals
-Molecular orbitals are formed due to sidewise overlapping of atomic orbitals on either sides of
the internuclear axis of bonded atoms. The electron density is concentrated on either side of the axis.
Bonding orbital is designated as , whereas antibonding orbital is designated as * .

Illustrations:
Chemical Bonding 34
Combination of two 'p' orbitals above and below the internuclear axis

+
+

+
+
+
- -
- - - -
p
bonding orbital

- -
+

+
-

+
+
-

+
- -
+

+
p*
anti bonding
orbital

DIFFERENCES BETWEEN AND MOLECULAR ORBITALS

S.No -Molecular orbital -Molecular orbital
1. Formed by end on overlapping along Formed by sidewise overlapping
the internuclear axis. perpendicular to the internuclear axis.
2. Large overlapped region. Small overlapped region.
3. Rotation about the internuclear axis is Rotation about the internuclear axis is
symmetrical. unsymmetrical.
4. Strong bonds are formed. Weak bonds are formed.

ELECTRONIC CONFIGURATIONS OF MOLECULES

1) The MO's are arranged in their increasing order of energy and filled with electrons.
2) The lowest available MO is filled first (Aufbau principle).
3) Each MO can accomodate a pair of electrons with opposite spins (Pauli's exclusion principle).
4) Pairing occurs only after all the degenerate MO's are filled with one electron each (Hund's rule).
5)The order of energy of homonuclear diatomic MO's upto nitrogen molecule is:
2 py *2 p y
1s *1s 2 s *2 s 2 px *2 px
2p *2 p
z z

But for elements heavier than nitrogen i.e., from oxygen onwards, the order will be as follows:
Chemical Bonding 35

2 p y *2 p y
1s *1s 2 s *2 s 2 px *2 px
2 p z *2 p z

MOLECULAR ORBITAL ENERGY LEVEL DIAGRAMS (MOED)

1) MOED of H2

*1s
Energy H H
1s 1s

1s
H2

* Electronic configuration of H2 molecule is 1s 2 *1s 2

number of bonding electrons - number of antibonding electrons

Bond order (B.O) =
2
2-0
= 1
2
* Hence there is a single bond between two atoms in H2 molecule.

2) MOED of N2
Chemical Bonding 36

*2 p x

*2 p y *2 pz

2pz 2py 2px 2px 2py 2pz

2 px

2 p y 2 pz

*2 s
Energy

2s 2s

2s

*1s

1s 1s

1s
N atom N2 molecule N atom

* Electronic configuration of N2 molecule is 1s 2 *1s 2 2 s 2 *2 s 2 2 p y 2 2 p z 2 2 p x2

10 - 4
* Bond order (B.O) = 3
2
* Hence there is a triple bond in N2 molecule.

2) MOED of O2
Chemical Bonding 37

*2 p x

*2 p y *2 pz

2pz 2py 2px 2px 2py 2pz

2 p y 2 pz

2 px

*2 s
Energy

2s 2s

2s

*1s

1s 1s

1s
O atom O2 molecule O atom

* Electronic configuration of O2 molecule is 1s 2 *1s 2 2 s 2 *2 s 2 2 px 2 2 p y 2 2 pz 2 *2 p y1 *2 pz1

10 - 6
* Bond order (B.O) = 2
2
* Hence there is a double bond in O2 molecule.
* It is paramagnetic due to presence of two unpaired electrons.

HYDROGEN BONDING
The electrostatic force of attraction between partially positively charged hydrogen in a polar
molecule and an electronegative atom is called hydrogen bond.
It is represented by dotted line.

Characteristics of Hydrogen bond

1) The hydrogen must be bonded to highly electronegative atom and should posses sufficient positive
charge to make hydrogen bond.
2) The electronegative atom should be smaller in size and possess high charge density to attract hydro-
gen.
CHEMICAL EQUILIBRIUM 1

CHEMICAL EQUILIBRIUM

Reversible reaction : A reaction which proceeds through forward and backward directions is called
reversible reaction. In a reversible reaction, reactants are converted into products and vice versa.
Eg.,

1) H2(g) + I2(g) 2HI(g)

2) CaCO3(s) CaO (s) + CO2 (g)

3) N2(g) + 3H2(g) 2NH3(g)

Irreversible reaction: A reaction that occur only in direction is called irreversible reaction i.e., only
reactants are converted to products and conversion of products to reactants is not possible.
Eg.,

1) CH4 (g) + 2O2 (g) CO2 (g) + 2 H2O (l)

2) 2KClO3(s) 2KCl(s) + 3O2(g)

Chemical equilibrium: The state at which the rate of forward reaction becomes equal to the rate of
backward reaction.

rate of forward reaction

state of equilibrium

rate of backward reaction

Characteristics of chemical equilibrium

1) At equilibrium, the rates of forward and backward reactions are equal.
2) The observable properties such as pressure, concentration, colour, density etc., of the system
remain unchanged.
3) Chemical equilibrium is a dynamic equilibrium, because both the forward and backward reactions
continue to occur.
4) Equilibrium can be reached by starting the reaction either from the reactants side or from the prod-
ucts side.
5) Pressure and concentration affect the state of equilibrium but do not change the equilibrium con-
stant. Where as, temperature can affect both the state of equilibrium and equilibrium constant.
6) A catalyst can increase the rates of both forward and backward reactions and helps in attaining the
equilibrium faster. But it does not affect the state of equilibrium.
CHEMICAL EQUILIBRIUM 2
Types of chemical equilibria
Chemical equilibria are classified into two types as homogeneous and heterogeneous.

Homogeneous equilibrium: A chemical equilibrium is said to be homogeneous if all the substances

(reactants and products) at equilibrium are in the same phase.
Eg.,

1) H2(g) + I2 (g) 2HI (g)

2) N2(g) + 3H2(g) 2NH3(g)

Homogeneous equilibrium: A chemical equilibrium is said to be heterogenous if all the substances at

equilibrium are not in the same phase.
Eg.,

1) CaCO3(g) CaO (s) + CO2 (g)

2) NH4HS (s) NH3(g) + H2S(g)

Law of mass action (proposed by Guld berg & Wage)

The rate of a reaction at an instant of time is proportional to the product of active masses of the
reactants at that instant of time under given conditions.

i) For dilute solutions, the molar concentrations are taken as active masses.
ii) For gases at low pressures, the partial pressures are taken as active masses.
iii) The active mass of a solid is taken as unity.

Equilibrium constant (Kc) in terms of concentration

Consider the following reaction at equilibrium,
aA + bB cC + dD
By applying law of mass action,

The rate of forward reaction v f [A]a [B]b

or v f =K f [A]a [B]b

The rate of backward reaction v b [C]c [D]d

or v b =K b [C]c [D]d

where [A], [B], [C] and [D] are the equilibrium concentrations of A,B,C and D respectively.
Kf and Kb are the rate constants of forward and backward reactions respectively.

But at equilibrium,
rate of forward reaction (vf) = rate of backward reaction (vb)
i.e., K f [A]a [B]b K b [C]c [D]d
CHEMICAL EQUILIBRIUM 3

K f [C]c [D]d
or =
K b [A]a [B]b

[C]c [D]d
or Kc =
[A]a [B]b
Kf
where K c = and is known as equilibrium constant.
Kb
product of concentrations of products at equilibrium
In general, Kc =
product of concentrations of reactants at equilibrium

Units of K c (mole.L-1 ) n
Where n = (c+d)-(a+b) = no. of moles of products - no. of moles of reactants

Relation between Kc and Kp

Kp is the equilibrium constant in terms of partial pressures. If A, B, C and D are gases then for
above reaction, Kp can be written as
PC c PD d
KP =
PA a PB b
where PA, PB, PC and PD are the partial pressures of A, B, C and D at equilibrium.
From ideal gas equation,
nRT
P= =CRT where C=molar concentration
V
[C]c [D]d
Therefore K P = a b
x[ RT ](c d )( a b)
[A] [B]

or K P =K c [RT]n
where n=(c+d)-(a+b) = no. of moles of gaseous products - no.of moles of gaseous reactants

If n=0 then K p =K c
and if n>0 then K p >K c
and if n<0 then K p <K c

Illustrations

1) H2(g) + I2(g) 2HI(g)

[HI]2
Kc =
[H 2 ] [I2 ]

PHI2
Kp =
PH . PI 2
2

K P =K c [RT]n
CHEMICAL EQUILIBRIUM 4
n=(2)-(1+1)=0
Kp = Kc

2) PCl5(g) PCl3(g) + Cl2(g)

[PCl3 ][Cl 2 ]
Kc =
[PCl5 ]

PPCl3 .PCl2
Kp =
PPCl 5
n = (1+1)-(1) = +1
Kp > Kc

3) N2(g) + 3H2(g) 2NH3(g)

[NH 3 ]2
Kc =
[N 2 ][H 2 ]3

PNH3 2
Kp =
PN2 .PH2 3

K P =K c [RT]n
n = (2) - (1+3) = -2
K p <K c

4) 2NH3(g) N2(g) + 3H2(g)

[N 2 ][H 2 ]3
Kc =
[NH3 ]2

PN2 .PH2 3
Kp =
PNH3 2

n = (1+3) - (2) = +1
Kp > Kc

5) CaCO3(s) CaO (s) + CO2 (g)

K c =[CO 2 ]
K p =PCO2
n=(1)-(0)=+1
Kp > Kc

Problems :
1) The molar concentrations of A, B & C at equilibrium for the reaction 2A + B 3C are 1,2
& 3 moles / litre respectively calculate Kc
CHEMICAL EQUILIBRIUM 5
2) Kc value of the following reaction is 0.4
H 2(g) + I2(g) 2HI(g)
if the equilibrium concentrations of H2 & HI are 0.2 and 0.8 moles/litre respectively. What is the
concentration of I2 at equilibrium.
3) The Kc of a reversible reaction is 5. if the rate constant of forward reaction is 2.5 what is the rate
constant for backward reaction.
4) Give the relations between Kc and Kp for the following reactions .

(i) CH 3COOC 2 H 5(aq) + NaOH (aq)
CH 3COONa (aq) + C 2 H 5OH (aq)

(ii) NH 4 HS(s)
NH 3(g) + H 2S(g)
5) For the following reversible reaction Kc is 0.5 L2/m2

N 2(g) +3H 2(g) 2NH 3 (g)
Calculate the Kp value at 270C.

Le Chatelier's principle
When external stress is applied on a system at equilibrium, the system shifts the position of
equilibrium so as to nullify the effect of stress.
Stress can be applied by changing the concentration or pressure or temperature. The effects of
these factors are discussed below.

Effect of concentration:
1) The forward reaction is favored when the concentration of reactants is increased.
2) The backward reaction is favored when the concentration of products is increased.

Effect of pressure:
1) When pressure is increased, the system tries to decrease the pressure by favoring the reaction in
which the number of moles of gaseous substances are decreased.
2) When pressure is decreased, the system tries to increase the pressure by favoring the reaction in
which the number of moles of gaseous substances are increased.

Effect of temperature:
1) When the temperature is increased, the endothermic reaction is favored.
2) When the temperature is decreased, the exothermic reaction is favored.

Industrial applications

Haber's process (synthesis of ammonia)

In this process, ammonia is synthesized from nitrogen and hydrogen gases. Le Chatelier's principle
can be applied to improve the yield of ammonia as follows.

N 2 (g) + 3H 2 (g) 2NH3 (g) ; H = -92 kJ
Effect of pressure: The number of moles gaseous substances decreases from (4 to 2) in the forward
reaction. Hence increase in pressure favors the synthesis of ammonia. In the industrial process, the reac-
tion is carried out at high pressures (200 atm).

Effect of temperature: Forward reaction is exothermic. Hence increase in temperature favors the
dissociation of ammonia. But at low temperatures the reaction does not occur. Hence the reaction is
carried out at moderate temperatures (725 - 775 K).
To increase the rate of reaction, finely powdered iron is used as catalyst and Mo is used as promoter.
CHEMICAL EQUILIBRIUM 6
Favourable conditions:
Pressure 200 atm
Temperature 725 to 775 K
Catalyst Fe
Promoter Mo

Contact process (industrial synthesis of SO3)

In this process, sulfur trioxide is synthesized by oxidizing sulfur dioxide. Le Chatelier's principle can
be applied to improve the yields as follows.

2SO 2 ( g )+ O 2 ( g )
2SO 3 ( g ) ; H = -189 kJ
Effect of pressure: The number of moles of gaseous substances decreases from (3 to 2) in the forward
reaction. Hence increase in pressure favors the formation of sulfur trioxide. But at high pressures, the iron
towers used in the reaction are corroded. To avoid this moderate pressures (10 atm) are employed.

Effect of temperature: Forward reaction is exothermic. Hence low temperatures favor the synthesis of
sulfur trioxide. But at low temperatures the reaction does not occur. Hence the reaction is carried out at
moderate temperatures (673 K).

To increase the rate of reaction, platinized asbestos or V2O5 are used as catalysts.
Favorable conditions
Pressure 10 atm
Temperature 673 K
Catalyst Pt or V2O5

TEST YOUR UNDERSTANDING

State whether the following statements are true or false.
1) A catalyst alters only the rate of forward reaction at equilibrium.
2) The forward reaction is favoured when pressure is increased on the following reaction system at
equilibrium.

A( g ) B( g )
2C( g )
3) The synthesis of ammonia is favoured by removing ammonia formed, in Haber's process, by liquefy-
ing it.
4) The value of equilibrium constant Kc can be changed by changing the temperature.
5) Kc > Kp for the following reaction.

Ca (OH ) 2 CO2( g )
CaCO3( s ) H 2O( aq )
 1

CHEMICAL KINETICS
Chemical kinetics deals with
1) Study of rates of reactions
2) Factors affecting rate of reaction
3) Study of mechanisms of reactions

Rate of reaction : The rate of reaction is defined as the change in molar concentration of either
reactants or products in unit time.
change in concentration
rate r =
time interval
Let dc is the decrease in concentration of reactants in a small interval of time dt then
dc
r=- ( negative sign indicates decrease in concentration )
dt
If dx is the increase in concentration of products in a small interval of time dt then
dx
r= ( positive sign indicates increase in concentration )
dt
E.g., For a reaction, A
B
d A d B
rate r
dt dt
In general for a reaction, pP + qQ rR + sS
the relations between rates of reaction with respect to P,Q,R and S can be written as
1 d P 1 d Q 1 d R 1 d S
- =- =+ =+
p dt q dt r dt s dt

Eg., for the reaction, N 2 g +3H 2 g

2NH3 g , the relations can be expressed as

d N2 1 d H2 1 d NH 3
- -
dt 3 dt 2 dt

Factors affecting the rate of reaction

1) Nature of reactants: Rate of a reaction depends on the nature of bonding in the reactants. Ionic
compounds react faster than covalent compounds.
The reactions between ionic compounds in water occur very fast as they involve only exchange of
ions.
Eg., AgCl is precipitated out immediately when AgNO3 solution is added to NaCl solution.
AgNO 3 +NaCl AgCl NaNO 3
This reaction involves only exchange of ions as shown below and hence occurs very fast.
Ag + +NO -3 +Na + +Cl- AgCl Na + NO -3
Reactions between covalent compounds take place slowly because they require energy for the
cleavage of existing bonds.
Eg., Following esterification of acetic acid occurs slowly as the breaking of bonds require energy.
O O
H2SO4
H3C C + H O C2H5 H3C C + H2O
OH OC2H5
 2
2) Concentration: Rate of a reaction is directly proportional to the concentration of reactants.
rate (r) cn
where c = concentration
n = order of the reaction
or r = kcn
where k = specific rate
The number of collisions increases with increase in concentration and hence the rate of the reaction
also increases.
The rate of a reaction decreases with time as the concentration of reactants is decreasing. This can
be shown graphically as follows.

concentration of reactants

Time

3) Temperature : The average kinetic energy and hence the number of collisions increase with abso-
lute temperature. Hence rate of reaction increases with increase in temperature.
Usually the rate of a reaction is doubled when the temperature is increased by 10oC.
Temperature Coefficient : The ratio of rate constants of a reaction at two different temperatures
which differ by 10oC is called temperature coefficient.
k t +10o C
Temperature coefficient = 2 to3
k t oC
The relation between rate constant and temperature can be shown by Arrhenius equation.
k = A.e-Ea/RT
Where k = specific rate constant
A = Frequency factor
Ea = Activation energy
R = Universal Gas constant
T = Absolute Temperature
Multiplying by 'ln' (natural logarithm) on both sides,
Ea
ln k = ln A-
RT
Ea
or 2.303 log k = 2.303 log A-
RT
Ea
or log k = log A-
2.303 RT
When a graph is plotted by taking log k on y - axis and 1/T on x-axis, a straight line with negative slope
is obtained.
Ea E
slope = - =- a where R = 1.987 cal / K / mole
2.303 R 4.576
 3

log A
Ea
slope = -
2.303 R

log k

1
T

Relation between two rate constants at two different temperatures can be given as
k2 Ea 1 1
log = -
k1 2.303R T1 T2

k2 E a T2 -T1
or log =
k1 2.303R T1T2

4) Catalyst: Catalyst is a substance which alters the rate of reaction without being consumed or without
undergoing any chemical change during the reaction.
A catalyst increases the rate of reaction by providing a new path with lower activation energy for the
reaction. In case of reversible reactions, catalyst lowers the activation energies of both forward and
backward reaction to the same extent and helps in attaining the equilibrium quickly.

without catalyst
Potential energy

in presence of catalyst

Reaction coordinate

Problems :
1) Write the relations between the rates with respect to reactants & products in the following reaction.
2N2O 2N2 + O2
Rate Equation or Rate Expression or Rate Law: Equation that describes mathematical dependance
of rate of reaction on the concentration terms of the reactants is called Rate Equation.

For a general reaction, xA+yB+zC products.

x y z
r = k A B C
where k= rate constant or specific rate
x,y and z are orders with respects to A,B and C respectively.

Order of reaction :Sum of the powers of the concentration terms in the rate equation is called order
of reaction.
For a general reaction, xA + yB + zC products.
 4
x y z
if the rate expression is r = k A B C
Then the order of this reaction is equal to x + y + z

Note: Order of a reaction is to be determined experimentally. It may have positive or negative or zero
or a fractional values.
In case of simple reactions, the order of reaction and hence the rate equation can be written
according to stoichiometric equation. But the actual rate law should be written by conducting experi-
ments.
Depending on the order of reaction, chemical reactions can be divided into zero, first, second &
third order reactions as follows.

Zero order reaction: Total order of the reaction is zero.

Example:
1) Decomposition of NH3 on metal surfaces such as gold and molybdenum.
Au
N 2 g +3H 2 g 2NH 3g
r = k[N2]0[H2]0

First order reaction: Total order of the reaction is one.

Examples:
1) Thermal decomposition of N2O5
N2O5 N2O4 + 1/2 O2
r = k[N2O5]
2) Thermal decomposition of SO2Cl2
SO2Cl2 SO2+Cl2
r = k [ SO2Cl2]
3) Thermal decomposition of H2O2
H2O2 H2O + 1/2 O2
r = k[H2O2]
4) All radioactive disintegrations

Second order reaction : Total order of the reaction is two.

Examples:
1) Thermal decomposition of N2O
2N2O 2N2 + O2
r= k [N2O]2
2) Decomposition of Cl2O
2Cl2O 2Cl2 + O2
r= k [Cl2O]2

Third order reaction : Total order of the reaction is three.

Examples:
1) Reaction between NO and O2 to give NO2
2NO + O2--------> 2NO2
r = k[NO]2[O2]
2) Reaction between NO and Cl2 to give NOCl
2NO + Cl2 2NOCl
r = k[NO]2 [Cl2]
 5
Problems :
1) What is the order of the reaction if the rate law for the reaction A + 2B products is
r = k [A]1/2[B]2

Rate constant (k): The rate of a reaction at the unit concentrations of all the reactants of the reaction is
called specific rate (or) rate constant.
rate = k when [reactants] = 1

Units of rate constant

For a general reaction, A products
Rate expression can be written as
dc n
rate = k A
dt
where n = order of the reaction
dc 1
k= x
dt A n

mole / litre 1
Units of k = x n
sec mole / litre
1-n

=
mole / litre
sec
= Ln-1 .mole
- n-1
.sec-1
For 1st order reaction sec

-1

For 2nd order reaction -1

L.mole sec

-1

For 3rd order reaction 2 -2

L .mole sec

-1

-1 -1
For zero order reaction mole .L sec

Molecularity
Elementary reactions: The chemical reactions which occur in one single step are called elementary
reactions.
But most of the reactions occur in more than one step. The sequence of elementary steps that occur
during a reaction is referred to as mechanism of that reaction.

Rate determining step: The elementary step or reaction with slowest rate is called rate determining step
or rate limiting step. The rate of overall reaction depends on this step.

Molecularity: Total number of atoms or molecules or ions taking part in an elementary reaction is called
molecularity of that elementary reaction (or step).
It is only possible to define the molecularity of an elementary step. But the molecularity of the overall
reaction which involves more than one step cannot be defined.
Molecularity is an integer. It cannot be zero or fractional. The maximum value observed is 3. It can be
deduced theoretically from the proposed mechanism
 6
Differences between Order and Molecularity

Order Molecularity
1) Sum of the powers of concentration terms 1) Total number of atoms or molecules or
in rate expression is called order. ions taking part in an elementary reaction is
called molecularity
2) It may have zero or positive or negative or 2) It can only have integral values (1,2 or 3).
integer or fractional values. Its value cannot be zero or fractional.
3) It is determined experimentally 3) It is deduced theoretically from the
mechanism of the reaction.

Integrated rate equations for zero and first order reactions

Zero order rate equation:
Reactions in which the rate is independent of the concentrations of reactants are called Zero order
reactions. The integrated rate equation for zero order reactions is derived as follows.
dc dx
- = =kco
dt dt
dx o
or =k a-x k
dt
or dx = k dt
or x = kt
x
or k=
t
Where k = specific rate
x = amount of reactant consumed or reacted in time 't'.
First order reaction
For a first order reaction R
P
Let
The initial concentration of reactant = a mol. dm-3.
Amount of reactant decomposed in 't' sec = x mol. dm-3.
The concentration of reactant after 't' sec = (a - x ) mol. dm-3.
dx
The rate at time 't' is proportional to the concentration of reactant (a - x) at that time. Since the
dt
reaction is a first order reaction,
dx
a-x
dt
dx
k a-x
dt
dx
=k.dt [where k = specific rate]
a-x
On integration
 7
dx
a-x k .dt
-ln (a-x) = k.t + c
when t = 0 then x = 0
-ln a = c

Hence -ln(a-x) = kt-ln a

a
or kt = ln
a-x
1 a
or k= ln
t a-x
2.303 a
or k= log
t a-x
Where a = initial concentration of reactant
x = concentration reacted in an interval of time 't'
(a-x) = concentration of reactant after time 't'

Half life (t1/2) of a reaction :The time required for initial concentration of reactants to become half is
called half life.

Half life of first order reaction can be derived as given below.

x = a/2 when t = t1/2
a
Then a-x = a- = a/2
2
2.303 a 2.303
Therefore k= log t log2 = 2.303 x 0.3010 ( log2 = 03010)
t1/2 a/2 1/2 t1
2

0.693
or t1/2
k

Methods of determination of order of a reaction :

1) Integrated equation method or Trial and error method
* The initial concentration (a) and the concentrations at various intervals of time (a - x) are measured
during the progress of reaction by suitable analytical methods. These values are substituted in the rate
equations of different rate orders. The order corresponding to the rate equations, which gives constant 'k'
values is taken as the order of reaction.
Rate equations
For a Zero order reaction R
P
x = kt
x a- a-x R o -R t
or k= = =
t t t
 8
For first order reaction R
P
2.303 a 2.303 R
k= log = log o
t a-x t Rt

For second order reaction 2R

P
1 x 1 R o -R t
k= = .
at a-x R o t R t

For second order reaction R1 + R2

P
2.303 b( a x )
k= log
t(a-b) a (b x )
The order can also be ascertained graphically as follows
For a zero order reaction, the graph of 'x' versus 't' must be a straight line parallel to time (t) axis.

a
For a first order reaction, the graph of log versus 't' should be a straight line with positive slope
a-x
and should pass through the origin

a
log
a-x

x
For a second order reaction, the graph of a a-x vs 't' must be a straight line passing through the

origin with a positive slope.

x OR b(a-x)
a(a-x) log
a(b-x)

t t

Half life method

is inversely proportional to a
Half life t 1
2
n-1
 9
1
t1
2 a n -1
where a = initial concentration
n = order

The order 'n' of a reaction can be calculated by comparing two half lives - t 1 & t 1 with initial
2 2

concentrations a & a respectively..

t 1 n -1
a
2
=
t1 a
2

3) Van't Hoff differential method

dc dc n
The rate - for a reaction of nth order is given by the equation, - =kc
dt dt
For two initial concentrations c1,c2, we have
dc1 dc 2
- =kc1n ; - =kc n2
dt dt
dc
log - 1 log k + nlogc1
dt
dc
log - 2 log k + nlogc 2
dt
dc dc
or log - 1 - log - 2 n log c1 nlogc 2 n log c1 logc 2
dt dt

dc dc
log - 1 - log - 2
n dt dt
log c1 logc2
For two different initial concentrations c1 and c2, the rates are determined at any given time from c-t graph.
These are substituted in the above equation and 'n' is calculated.
concentration of reactants

concentration of reactants

c1
c2

Time (t) Time (t)

4) Ostwald's Isolation Method

In this method, order with respect to each reactant is determined separately by taking other reactants
in larger quantity.
For example, for the given reactions A + B products, the order is determined as follows:
1) First the concentration of 'B' is taken in larger excess and the order (nA) with respect to 'A' is deter-
mined by any of the other three methods.
 10
2) In the second experiment the order (nB) with respect to 'B' is determined by taking 'A' in large excess.
The order of the overall reaction is taken as nA + nB.

Kinetic Molecular Theory of Reaction Rates or Collision theory of reaction rates :

This theory was proposed by Arrhenius. The main postulates of this theory are
1) Chemical reactions occur due to collisions between reactant molecules.
2) But all the collisions do not lead to the formation of products.
3) Only those collisions taking place between molecules possessing certain minimum amount of energy
can form the products. This minimum amount of energy is called Threshold Energy (ET).
4) The energy possessed by the normal molecules under STP conditions is called 'Average Energy'. The
difference between threshold energy and average energy of the reacting molecules is called Activation
energy (Ea).
Ea = Threshold energy (ET) - Average energy (ER)
5) Some molecules will get threshold energy during collisions and are called activated molecules and
denoted by asterick(*).
6) The collisions taking place between activated molecules are called activated collisions. The reaction
occurs only during the activated collisions.
Activated molecules constitute a small fraction of total molecules. Similarly activated collisions consti-
tute small fraction of total collisions. Hence all the chemical reactions do not occur in fraction of second.
A+A A* + A
A* + A*
products

Where A = normal molecule

A* = Activated molecule
7) The number of binary collisions per unit time (Z) is given by

2 8 kT
Z AB .n A .n B

where AB = Collision diameter
= reduced mass
n A & n B are number of molecules of A & B
8) The relation between specific rate (k), temperature (T) and activation energy Ea can be given as follows
k = A.e -Ea /RT
or
k = p.Z.e-Ea /RT
where p = probability factor
The concept of activation energies of both forward and backward reactions (Ea and Ea') can be
shown graphically as follows.
 11

Energy barrier
ET

Ea E1a
ET
ER
H
Ep

Where ER = Energy of reactants

EP = Energy of products
ET = Threshold energy
Ea = Activation energy of forward reaction
Ea1 = Activation energy of backward reaction
H = Enthalpy of reaction

Problems :
1) The rate constant of a first order reaction is 1.386 sec-1. What is it's half life.
2) The initial concentration of A is 0.5 moles/litre. If the concentration becomes 0.25 mole/litre in 5 sec.
What is the value of rate constant.

TEST YOUR UNDERSTANDING

State whether the following statements are true or false.

1) The rate of a reaction increases with time as the concentration of reactants decreases.
2) The order of a reaction is always determined experimentally.
3) The units of rate constants for the following reaction are (L / mol /sec).
2NO(g) + Cl2 (g) 2NOCl (g)
4) The half life of zero order reaction is proportional to the initial concentration.
5) The rate of consumption of hydrogen gas is thrice of formation of Ammonia in the following reaction.
N2 (g) + 3H2 (g) 2 NH3 (g)
6) In Ostwald isolation method, the reactant for which the order is going to be determined is taken in
excess when compared to the concentrations of other reactants.
7) A positive catalyst increases the activation energy of both forward and backward reactions.
8) In exothermic reaction the activation energy of forward reaction is always greater than that of back
ward reaction.
a
9) For a second order reaction, a straight line is obtained when log is plotted against time (t)
ax
10) Rate of reaction increases with increasing temperature as the threshold energy increases.
Electrochemistry 1

ELECTROCHEMISTRY
* Electrochemistry deals with
1) The processes in which electrical energy is converted to chemical energy.
2) The processes in which chemical energy is converted to electrical energy.
3) Preparation of metals and alloys using electricity.

Based on electrical conductivity, substances are divided into two types.

i) Conductors - which can conduct electricity.
e.g. Al, Cu, Fe, Graphite etc...
ii) Insulators - which resist the conduction of electricity.
e.g. Diamond, Glass, Plastics etc....

The electrical conductors are again divided into two types as follows;
i) Metallic or electronic conductors:- The conductors which conduct the electricity through the elec-
trons.
e.g. All metals, Graphite etc...
* No chemical reaction occurs during the conduction of electricity.
* Conductivity decreases with increase in temperature due to vibrational disturbances.

ii) Electrolytes :- The substances which furnish oppositely charged ions for the conduction of electricity.
e.g :- NaCl, KCl, CH3COOH, HCl etc.......
* There is flow of ions towards the oppositely charged electrodes.
* During conduction of electricity through electrolytes, oxidation occurs at anode whereas reduction
occurs at cathode i.e., a chemical reaction occurs.
* The conductivity increases with increase in temperature as the extent of ionization increases.

Non electrolytes :- The substances which do not furnish ions for electrical conduction are called non -
electrolytes.
e.g : urea, glucose, sucrose etc. ...
Strong electrolytes : undergo complete ionization in water
e.g. NaCl, KCl, K2SO4, HCl, H2SO4,NaOH, NaNO3 etc....
Weak electrolytes : under go partial ionization in water
e.g. HF, CH3COOH, NH4OH, HCOOH etc....

Resistance and ohm's law :- According to Ohm's law, resistance (R) offered by an electrolyte in a
solution is proportional to length (l) and inversely proportional to the cross sectional area (a) of electrodes.
length (l )

Resistance (R) area (a)

l
i.e., R
a
l
or R=s.
a
Where s = specific resistance (resistivity)
Electrochemistry 2
a
s = R. l
When a = 1 cm2 and l = 1 cm
Then s=R
Specific resistance (s) : The resistance shown by a material of 1 cm length and 1 cm2 of cross sectional
area is called specific resistance (or) resistivity.

Units of 's'
a
s=R.
l
cm 2
ohm .
cm
ohm . cm. (in CGS)
or ohm . m (in SI)

Conductance (C) :- It is the reciprocal of resistance.

1
C=
R
1 a
C= x
s l
a
C=kx
l
1
Where k= = specific conductance (conductivity)
s
l
Cell constant : The quantity, is called cell constant.
a
distance between two electrodes l
cell constant =
area of cross section of electrodes a
Specific conductance (k) :- The conductance of 1 cm3 solution is called specific conductance or
conductivity.
Units of 'k' = ohm-1 cm-1 or mho cm-1 (C.G.S)
. -1
= Siemen m or S.m -1
(S I)

Equivalent conductance ( ) :- The conductance of a solution containing one equivalent weight of

electrolyte present between two parallel electrodes separated by a unit distance of 1 cm (or) 1 m is called
equivalent conductance ( ).
k x 1000

N
Where N = Normality
k = Specific conductance
Units of ' '
Ohm-1. cm -1

equivalents . cm -3
Electrochemistry 3
= ohm-1 cm2 equivalents-1 (CGS)
or = Siemen. m2. equivalent -1 (S I)
Molar conductance ( or m ) :- The conductance shown by a solution containing 1 mole of electrolyte
present between two parallel electrodes separated by a unit distance of 1 cm or 1m is called molar
conductance
k x 1000

M
M = Molarity
Units : ohm-1. cm2. mol-1
or Siemen . m2 . mol-1
Factors affecting conductivity of electrolytes :
* Strong electrolytes undergo complete ionization and hence show higher conductivities whereas
weak electrolytes undergo partial ionization and hence show low conductivities in their solutions.
* The ionic mobility decreases with increase in its size and hence conductivity also decreases.
* In aqueous solutions the extent of hydration affect the mobility of the ion, which in turn affect the
conductivity. Heavily hydrated ions show low conductance values.
E.g.,In aqueous solutions Li+ ion (with high charge density) is heavily hydrated than Cs+ ion (with low
charge density). Hence hydrated Li+ bigger than hydrated Cs+ . As a result, lithium salts show lower
conductivities compared to those of cesium salts in water.
* Specific conductance (k) decreases with decrease in concentration of solution as the number of
ions per unit volume decreases.
* Equivalent or molar conductances increase with decrease in concentration (upon dilution) as the
extent of ionization increases
* Weak electrolytes undergo complete dissociation at infinite dilution and show the maximum con-
ductance. The equivalent conductance and molar conductance of solutions at infinite dilutions are denoted
by
(or) 0 and (or) o respectively..

Debye - Huckel - Onsagar equation

It is possible to determine the equivalent conductances of electrolytes at given concentration by using
Debye - Huckel - Onsagar equation.
c = o A c
Where c = equivalent conductance at given concentration.
o = equivalent conductance at infinite dilution.
c = concentration
82.4 8.2 x 105
A = a constant = 1
+ 3
o
DT 2 DT 2
D = Dipole moment of water
A straight line with negative slope is obtained when equivalent conductance values are plotted against
different concentrations. The equivalent conductance at infinite dilution can be determined by extending
this straight line to zero concentration.
Electrochemistry 4

Conductance ratio ( ) : The ratio of the equivalent conductance ( c ) at given concentration to that at
infinite dilution ( o ) is called conductance ratio ( )
c

o
For weak electrolytes, ' ' is called degree of ionization.

KOHLRAUSCH LAW OF INDEPENDENT MIGRATION OF IONS

The equivalent conductance of an electrolyte at infinite dilution is the algebraic some of equiva-
lent conductances of constituent ions (cations and anions) at infinite dilution.
electrolyte

= +
= equivalent conductance of cation at infinite dilution
= equivalent conductance of anion at infinite dilution
and are also called ionic conductances at infinite dilution. These are proportional to ionic
mobilities u o+ and u -o .
i.e., u +o and u -o
or + k u +o and - = k u -o
'k' is a proportionality constant and its value is equal to one Faraday (96,500 coulombs)
+ = F u o+ and - = F u -o
Hence Kohlrausch law can be written as
electrolyte
F u +o F u -o
or
electrolyte
F u +o u -o
Applications :
1) It is not possible to experimentally determine the equivalent conductances of weak electrolytes at
infinite dilution. But by using this law it is possible to calculate the equivalent conductance of weak electro-
lytes at infinite dilution.
The equivalent conductance of acetic acid at infinite dilution can be calculated as follows
- +
e.g. CH

3COOH
CH 3COO H
- +
CH

3COONa
CH3COO Na
+ -
HCl
H Cl

+ -
NaCl Na
Cl
Electrochemistry 5
CH3 COOH CH 3 COONa HCl
Therefore NaCl
2) The degree of ionization of a weak electrolyte ( ) can be calculated by using Kohlrausch law as
follows.
equivalent conductance of solution of given concentration ( c )
Degree of ionization ( ) =
equivalent conductance of solution at infinite dilution ( )

c
i.e.,

Problems:-
1) At 250C, the specific conductance of acetic acid of 0.01N concentration is 0.000163 ohm-1 cm-1. What
is c at this concentration ?
2) At 250C, the equivalent conductances of CH3COONa, HCl and NaCl at infinite dilution respectively
are 91.0, 426.16 & 126.45 ohm-1. cm2. eq-1. What is o of CH3COOH ?
3) c of acetic acid at 250C is 16.3 ohm-1 cm2 eq-1. The ionic conductances of H+ and CH3COO - are
349.83 & 40.89 ohm-1 cm2 eq-1. What is of CH3COOH ?

ELECTROLYSIS
The decomposition of chemical compound in the molten state or in solution state into it's constituent
elements under the influence of an applied E.M.F is called electrolysis.
Electrolysis is carried out in an electrolytic cell, provided with two electrodes. The electrode con-
nected to negative end of a battery is called cathode and which is connected to positive end is called
anode.
An electrolyte either in molten state or in solution state is taken into this cell and electrolyzed by
applying E.M.F. The cations are reduced at cathode and anions are oxidized at anode.

Battery
+ e-
e-

Anode + - cathode

electrolyte

Examples:
Electrolysis of molten KCl
Following reactions will occur at electrodes when molten KCl is electrolyzed using platinum elec-
trodes.
KCl K + + Cl-

molten
At cathode
K + +1e-
K Reduction
At anode
2Cl-
Cl 2 2e - oxidation
Electrochemistry 6
Complete redox reaction
2KCl
2K + Cl 2

Electrolysis of aqueous solution of KCl

In this case, hydrogen gas is evolved at cathode as K+ ions can not undergo reduction in presence of
water. The electrode reactions are shown below.
K + (aq) + Cl-(aq)
KCl(aq)
At cathode
2H 2 O + 2e-
H 2 + 2OH -
At anode
Cl 2 2e
2Cl-
Overall reaction is
2KCl + 2H 2 O H 2 + 2KOH + Cl 2
Electrolysis of water
Following reactions will occur during the electrolysis of water.
At cathode
4H2O + 4e-
2H2 + 4OH-
At anode
O2 + 4H+ + 4e-
2H2O
Net reaction
2H2O 2H2 + O2
Hence 4 Faradays of electricity is required to electrolyze 2 moles of water.

Some important aspects in electrolysis

1) The ions of highly reactive metals like alkaline and alkali earth metals do not undergo reduction in
presence of water. These metals have low reduction potentials than water and hence, water molecules
undergo reduction by liberating H2 gas at cathode.
2) The metals with low reactivity, like transition metals, can undergo reduction even in presence of
water. These metals have higher reduction potentials than water.
3) Oxy anions like SO-24 , NO3- , CO32- , PO3-4 etc. are very stable and can not undergo oxidation at
anode. Instead water molecule is oxidized by liberating oxygen gas.
E.g., In the electrolysis of aqueous solution of AgNO3 by using platinum electrodes, silver can be
deposited at cathode as it is less reactive metal. But NO3- ion cannot be oxidized. Instead, water is
oxidized by liberating oxygen gas.
Ag + (aq) NO3- (aq)
AgNO3 (aq)

At cathode: Ag + (aq) 1e -
Ag

At anode: 2H 2 O 4H + + O 2 + 4e -
4) Electrodes which do not participate in the electrochemical reaction are called inert or passived
electrodes. Usually platinum and graphite electrodes are used as inert electrodes.
But some electrodes may participate in the electrochemical reaction. These are said to be active
electrodes.
e.g. When aqueous solution of AgNO3 is electrolysed by using copper electrodes, silver is deposited
at cathode and dissolved at anode.
Electrochemistry 7
+ -
At cathode: Ag (aq)
1e
Ag Deposition of silver on cathode

At anode: Ag + (aq) 1e-

Ag Dissolution of silver anode
In this case, silver electrode is acting as active electrode.

FARADAY'S LAWS OF ELECTROLYSIS

First law : When an electrolyte, either in molten state or solution state is electrolyzed, the amount of
substance deposited or dissolved at electrodes is directly proportional to the quantity of electricity
passed through the electrolyte.
Mathematically
amount of substance (m) quantity of electricity in coulombs (q)
mq
m eq
Where e = electrochemical equivalent
But q = ct
Where c = current in amperes
t = time in seconds
m = ect

When q = 1 Coulomb or when c=1 ampere and t = 1 sec

Then e=m
Hence
Electrochemical equivalent :- The amount of substance deposited or liberated or dissolved at elec-
trodes when 1 coulomb of electricity is passed through the electrolyte in molten or solution state is called
electrochemical equivalent of that substance.
or
The amount of substance deposited or liberated or dissolved at electrodes when 1 ampere current
is passed through the electrolyte in molten or solution state for one second is called electrochemical
equivalent of that substance.

Faraday :- The amount of charge transported during the migration of 1 mole of electrons is called
Faraday.
Faraday (F) = 1.602 x 10-19C x 6.022 x 1023
= 96,500 coulombs

Equivalent weight (E) :- The amount of substance formed at electrodes when one Faraday of electricity
is passed through the electrolyte.
Hence E=Fxe
E
or e=
F
Ect Eq
m or m
F F
Atomic weight
Where E=
Valency

Faraday's Second law :- If the same quantity of electricity is passed through different electrolytic cells
Electrochemistry 8
connected in series containing different electrolytic solutions or melts, the amounts of substances deposited
or liberated or dissolved are directly proportional to their equivalent weights.
mE
m1 E
or 1
m2 E2
Illustration :- When three electrolytic cells containing different electrolytes i.e., CuSO4 , AgNO3 and
H2SO4 in aqueous solutions are connected in series and same quantity of electricity is passed through
them, then from Faraday's second law the ratio of amounts of Cu, Ag, H2 and O2 formed at different
electrodes can be given as follows.
m Cu : m Ag : m H 2 : m O 2 = E Cu : E Ag : E H2 : E O2

mCu E
or Cu
mAg E Ag

mH2 EH2
or
mO2 EO 2

mCu E
or = Cu etc. .....
m O2 E O2

Battery

+ - + - + -

CuSO4 AgNO3 H2SO4

Problems :
1) A current of 10 amperes is passed through molted AlCl3 for 96.5 sec. Calculate the mass of
aluminium deposited at cathode.
2) What is the ratio of weights of Ag and Al deposited at respective cathodes when the same current
is passed for same period through aqueous AgNO3 and Al2(SO4)3 solutions.

GALVANIC CELLS (OR) VOLTAIC CELLS

The device which makes use of a spontaneous redox reaction for the generation of electrical energy
is called galvanic cell or voltaic cell or electrochemical cell.

Construction of a galvanic cell : A galvanic cell consists of two half cells called single electrodes which
are connected to each other.
Single electrode: A single electrode consists of a metal or a non metal in contact with their ions.
While representing a single electrode, the metal or non metal and its ion are written by separating with
a vertical line.
e.g: Metal electrodes
Zn2+ / Zn
Cu2+ / Cu
Electrochemistry 9
Ag+ / Ag

Non Metal electrodes

1
H+ H 2 , Pt
2
Cl2, Pt / Cl-
Br2, Pt / Br-
Daniel cell :
This cell contains two half cells divided into two compartments by a porous diaphragm. A zinc rod
immersed in ZnSO4 solution in one half cell acts as anode. Another half cell is provided with a copper rod
immersed in CuSO4 solution. It acts as cathode. These are connected by a metallic wire externally.
When connected, following reactions occur in the two half cells and thus by producing electricity.

In Zn half cell (anode) Zn Zn+2 + 2e- oxidation

In Cu half cell (cathode) Cu2+ + 2e- Cu Reduction

Total reaction Zn + Cu+2 Zn2+ + Cu

Note: In galvanic cell, anode is indicated by negative sign whereas cathode is indicated by positive sign.

Reactive resistance
Ammiter
e-

e- e-

Anode Cathode
Zn rod Cu rod

Zn-2 Cu+2
CuSO4 solution
ions ions

ZnSO4 solution
Porous diaphragm

Voltaic cell :
Daniel cell is modified by connecting two half cells internally by a salt bridge. One half cell contains a
zinc rod immersed in ZnSO4 solution and another half cell consist of a copper rod immersed in CuSO4
solution.
These two half cells are connected externally by a metallic wire whereas a salt bridge is used to
connect them internally.
Salt bridge is a U-shaped tube filled with Agar - Agar solution of KCl or NH4NO3. This is used to
avoid junction potential.
Following reactions occur in this cell.
In Zn half cell (anode) Zn Zn+2 + 2e- oxidation
In Cu half cell (cathode) Cu2+ + 2e- Cu Reduction

Total reaction Zn + Cu+2 Zn2+ + Cu

Electrochemistry 10

Ammeter
e- Reactive resistance
e-

e-
e-

Anode cathode

salt bridge
Electrolyte - I Electrolyte - II

Anode half cell Cathode half cell

Representation of galvanic cell :- According to IUPAC convention the oxidation half cell is written on
the left hand side and reduction half cell is written on the right hand side. Two vertical lines are used to
indicate the salt bridge. Negative sign is used to indicate the oxidation half cell (anode) and a positive sign
is used to indicate the reduction half cell (cathode).
e.g : Above galvanic cell can be represented as follows.
Zn / Zn2+ // Cu2+ / Cu
Where Zn / Zn2+ = Zn half cell
2+
Cu / Cu = Cu half cell
// = salt bridge

Differences between electrolytic and galvanic cells

Electrolytic cell Galvanic cell

1) Electrical energy is converted to chemical 1) Chemical energy is converted to electrical
energy energy.
2) A non spontaneous reaction is carried out by 2) A spontaneous reaction occurs.
using electrical energy.
3) Anode is indicated by positive sign whereas 3) Anode is indicated by negative sign whereas
cathode is indicated by negative sign. cathode is indicated by positive sign.
4) Both oxidation and reduction reactions occur 4) Oxidation and reduction reactions occur in
in one cell different half cells.

Note: 1) Oxidation occurs at anode and reduction occurs at cathode in both the cells.
2) The flow of electrons is always from anode to cathode in both the cells.
Single electrode potential (E) :- The potential difference existing at the surface of contact between
metal (or) non metal and its ionic solution is called single electrode potential.

Standard electrode potential (E0) :- The potential difference at the surface of contact between metal
(or) non metal and its ionic solution at unit concentration and at 250C is called standard electrode potential
(E0).
Single electrode potential can be written for oxidation half cell or reduction half cell. Both oxidation
electrode potential and reduction electrode potential have same magnitude but have opposite signs.
e.g : Zn / Zn2+ is oxidation half cell and its E0 value is + 0.762V.
Zn2+ / Zn is reduction half cell and its E0 value is - 0.762V.

Standard hydrogen electrode (SHE) (or) Normal hydrogen electrode (NHE)

In this cell, hydrogen gas at 1atm pressure is continuously bubbled into an acid solution of unit activity
( 1M HCl ) along a platinum rod, which is coated by platinum black.
Electrochemistry 11
The platinum rod is surrounded by a glass tube consisting of two circular holes. The glass tube is
immersed in the solution such that these holes are half exposed to air.
1
H H+ + 1e-
2 2(g) (aq)
The electrode potential of this cell is arbitrarily taken as Zero.
Eo 1 = 0 volts
H + (1M) H 2 (1atm)
2

This electrode is taken as primary reference electrode.

H2 (1 Atm)
Pt rod
hole

1M HCl

Black Pt foil

EMF of galvanic cell : The potential difference between two different electrodes in the galvanic cell is
called EMF of that cell.
E Cell = E Reduction - E Oxidation
half cell half cell

E Cell = ER - EL
According to IUPAC convention, EMF of a galvanic cell is calculated by substraction of the reduc-
tion electrode potential of left hand cell from that of right hand cell.
E Cell = E Right - E Left

Electrochemical series :- The standard reduction electrode potentials of various electrodes are deter-
mined relative to that of SHE.
These electrodes are arranged in their increasing order of standard reduction potentials in a series
called as electrochemical series.
In this series, the electrodes with negative Eo values are placed above hydrogen electrode whereas
the electrodes with positive Eo values are placed below hydrogen electrode.

Applications of electrochemical series

1) The elements with low reduction potential values are good reducing agents and those with high
reduction potentials are good oxidizing agents.
e.g. 'Li' with very low reduction potential is a reducing agent
'F2' with high reduction potential is an oxidizing agent
2) Metals with high negative potentials can displace metals with low negative potentials or high posi-
tive potentials
e.g. 'Zn' can displace metals beneath it in the series from their ionic solutions.
Zn + CuSO4 Cu + ZnSO4
3) Nonmetals with high reduction potentials are good oxidizing agents and can displace non metals
with low reduction potential values from their compounds.
e.g. F2 can displace Cl2 from NaCl
Electrochemistry 12
F2 + 2 NaCl 2 NaF + Cl2
4) A proper short hand notation for the galvanic cell can be written. While writing the galvanic cell , the
electrode with higher reduction potential is written on the right hand side and considered as cathode
(reduction half cell) and another electrode with lower reduction potential is written on the left hand side and
considered as anode (oxidation half cell)

Problems
1) Construct a galvanic cell containing two electrodes Ag+ / Ag and Zn2+ / Zn calculate the EMF of cell.
Write the cell reactions.
Eo for Ag+ / Ag = + 0 .799 volts
Eo for Zn2+ / Zn = - 0 .762 volts

NERNST EQUATION
The electrical energy (nFE cell ) produced in a reversible galvanic cell is equal to the decrease in Gibbs
free energy ( G)
Hence G = - nFEcell
Where n = no. of electrons transferred in redox reaction
F = Faraday
E = EMF of the cell
Under standard conditions
Go = - nFEocell

Consider the following equilibrium for a redox reaction occurring in a Galvanic cell;

aA + bB
cC + dD
For above reaction, the equilibrium constant from law of mass action can be written as
c d
C D
(Kc) = a b
A B
From laws of thermodynamics, the relation between Gibbs free energy and equilibrium constant (Kc)
is given as
G = G o + RTlnK c
nFE nFE o + RTlnK c
RT
-E = -E o + ln K c
nF
RT
E Eo ln K c
nF
2.303RT
E Eo log K c
nF
c d

EE
2.303RT
o
. log
C D
a b
nF A B
2.303RT product of equilibrium conc. of products
E Eo . log
nF product of equilibrium conc. of reactants
Electrochemistry 13
This equation is also applicable to single electrodes.

For metal or anode electrodes represented by Mn+ / M

Mn+ + ne- M
[M]
Kc =
[M n+ ]
2.303RT [M]
E = Eo - . log n+
nF [M ]
But [M] = 1
2.303RT 1
E = Eo - . log n+
nF [M ]
0.059 1
E = Eo - . log n+
n [M ]
0.059
E = Eo + . log[M n+ ]
n
For non metal or cathode electrodes represented by A / An-

A, Pt + ne-
An-
[A n- ]
Kc =
[A,Pt]
0.059
E = Eo - .log[A n- ] [ (A, Pt)=1]
n
0.059 1
E = Eo + . log n-
n [A ]
Problems :
1) Calculate EMF of the cell constructed by using electrodes Cl-(0.1 M) / Cl2,Pt and Ni / Ni2+ (0.01 M)
write the cell reactions
2) Calculate the potential of single electrode Zn++(aq) / Zn ? (0.1 M) (Eo =- 0.762V)
3) Calculate the electrode potential of the single electrode ? Cu2+ (C = 0.01 M) /Cu ? Eo = 0.337V)
4) Calculate the electrode potential of the single electrode. Ag+ (0.01 M) / Ag ? (Eo = 0.799V)

Battery or cell : It is a galvanic cell which is used as source of electrical energy. These are of two types
viz., 1) Primary cells, 2) Secondary cells

1) Primary cell
It is an electrochemical cell which acts as a source of electrical energy without being previously
charged up by an electric current from an external source.
In this cell, the reaction occurs only once and it becomes dead after using over a period of time. This
cell cannot be reused again as the reaction cannot be reversed.
E.g.,

1) LACLANCHE CELL
It consists of a carbon rod placed in a porous pot containing a mixture of MnO2 and carbon powder.
It acts as cathode whereas an amalgamated zinc acts as anode. The porous pot and zinc rod are placed in
20% NH4Cl solution.
Electrochemistry 14
Following reaction occur in this cell
At cathode :
2MnO 2 2H 2O 2e
2MnO OH 2OH

MnO 2 NH 4 e
MnO OH NH3
At anode :
Zn 2 2e
Zn
Zn 2 2OH + 2MnO OH
Zn 2MnO2 2H 2 O
Some secondary reactions are
2NH 4 Cl 2OH
2NH 3 2Cl 2H 2O

Zn 2 2NH 3 2Cl Zn NH 3 2 Cl2

It does not maintain steady current for long periods. Its voltage is 1.5 V. This cell cannot be recharged
after its use.

- +
C
Amalgamated Zn
porous pot
Glass Jar
C+MnO 2
mixture
20% NH4Cl
solution

2) DRY CELL
It is a modified Laclanche cell. It consists of a cylindrical zinc vessel acting as anode (negative elec-
trode). It is covered with a cardboard and sealed with pitch. A carbon rod acting as cathode (positive
electrode) is introduced at the centre of Zn vessel. It is surrounded by a paste of (C+MnO2). The remain-
ing empty space is filled with NH4Cl + ZnCl2 paste. These two pastes are separated by a porous sheet.
Following reaction occur in this cell
At cathode :
2MnO 2 2H 2O 2e
2MnO OH 2OH

MnO 2 NH 4 e
MnO OH NH3
At anode :
Zn 2 2e
Zn
Zn 2 2OH + 2MnO OH
Zn 2MnO2 2H 2 O
Some secondary reactions are
2NH 4 Cl 2OH
2NH 3 2Cl 2H 2O

Zn 2 2NH 3 2Cl Zn NH 3 2 Cl2

It does not maintain steady current for long periods. Its voltage is 1.5 V. This cell cannot be
recharged after its use.
Electrochemistry 15

Carbon rod
(cathode)

MnO2+
Zinc cup carbon black
(anode) +NH4 Cl paste

SECONDARY CELL
The cell in which electrical energy from an external source is first converted to chemical energy and
then made to operate in opposite direction by removing the external source.
In this cell, the reaction can be reversed practically. It can be recharged after its discharging.
E.g., 1) Acid storage cell (lead accumulator)
2) Alkali storage cell ( Edison battery)

LEAD ACCUMULATOR
Lead accumulator is an acid storage secondary cell which can be charged and discharged for several
times.
It consists of two lead electrodes
Anode ------- made by sponge lead
Cathode ----- Lead coated with PbO2
It can be represented as

Pb H2SO4 PbO2

or

Pb PbSO4(s), H2SO4 (aq), PbSO4 (s), PbO2 (s) Pb

Double Sulphation Theory :

According to this theory, proposed by Glasstone and Traube, following reactions occur at electrodes.
At Left Hand side electrode (Anode)
Pb

Pb 2+ + 2e (Oxidation)

Pb 2+ + SO 2-4
PbSO 4 s

Net Reaction Pb s + SO 2-4

PbSO 4 s 2e

At Right Hand side electrode (cathode)

PbO 2 + 2H 2O

Pb 4+ + 4OH

Pb 4+ + 2e

Pb 2+ reduction

Pb 2+ + SO 24

PbSO 4 s
Electrochemistry 16
- +
4OH + 4H
4H 2O
Net Reaction PbO 2 + 4H + + SO 2-4 + 2e

PbSO 4 s + 2H 2 O

Complete cell reaction for 2 Faradays is

Pb +
discharge
PbO2 + 2H 2SO4
charge
2PbSO4 + 2H2 O
In the discharging process, equal amount of water is formed in place of sulfuric acid. After charging
the lead accumulator, sulfuric acid is formed again. Hence the specific gravity of H2SO4 is changed during
charging and discharging processes. The voltage of the cell is changed from 2.15 V (40% H2SO4) to 1.88
V (5% H2SO4) during the discharging process.

FUEL CELLS
A fuel cell is a galvanic cell in which the chemical energy of fuel-oxidant system is converted
directly into electrical energy.
In fuel cells, the fuel and oxidant are supplied continuously on to the two different electrodes. The fuel
is oxidized at the anode and the oxidant is reduced at cathode. Theoretical efficiency of fuel cells is 100%.
Fuels used may be gases or liquids. E.g., H2, alkanes, carbon monoxide, Methanol, Ethanol, hydra-
zine, formaldehyde etc.,
Oxygen, air, hydrogen peroxide, nitric acid etc., are used as oxidants.
Platinum, porous PVC or PTFE (Teflon) coated with silver, nickel boride, raney nickel etc., can be
used as electrodes.

Examples
H2 - O2 Fuel cell
In this fuel cell, hydrogen and oxygen gases are continuously bubbled over porous carbon electrodes
suspended in concentrated NaOH solution. These electrodes are embedded with finely divided Pt or Pd
catalysts.
Electricity is produced due to the following reactions occurring at electrodes.
- -
At cathode: O 2 (g) + 2H 2O (l) + 4e 4OH
- -
At anode: 2 x [ H2 (g) + 2OH (aq) 2H2O (aq) + 2e ]

Overall reaction: 2H2 (g) + O2 (g) 2H2O (l)

The heat of formation of water is directly converted to electrical energy.

Hydrocarbon - O2 fuel cell

In these cells, hydrocarbons are used as fuels. Pure oxygen is used as oxidant. The electrodes are
made up of platinum. The electrolyte used is phosphoric acid instead of KOH.

Advantages of fuel cells

1) High efficiency of energy conversion process (nearly 100%)
2) Absence of moving parts in the cell eliminate wear & tear problems.
3) Silent operation.
4) Absence of harmful waste products.
5) Pure H2O is formed in the fuel cells used in space crafts and can be used for drinking purposes by
space travellers. Gemini and Apollo used these successfully.
Electrochemistry 17
CORROSION
The natural tendency of conversion of a metal into its mineral upon interaction with the environment
is called as corrosion.
E.g.
1) Rusting: Conversion of iron into its oxide (Fe2O3 - Heamatite)
2) Tarnishing: Silver is converted to its sulphide (Ag2S- silver glance)
3) Conversion of copper to its green colored carbonate (malachite)
Mechanism of corrosion
Corrosion may be a chemical or an electrochemical process. It is considered as anodic dissolution of
metal due to oxidation.
M M n+ + ne-
Hence the corrosion occurs under the conditions which favor the formation of voltaic cell with the
metal acting as anode.
Electrochemical corrosion is of two types as follows.

1. Hydrogen evolution type

Metals with more negative reduction potentials than that of hydrogen can undergo oxidation by liber-
ating hydrogen gas from aqueous solutions.
The electrode potentials of metal and hydrogen depend on PH, nature of metal and impurity. Hence
the corrosion also depends on these conditions.
E.g. Pure zinc does not undergo corrosion in salt solution or in neutral conditions. But it undergoes
corrosion in presence of Cu as impurity or in 2M acid solutions.

2. Differential oxygenation type

A metal can undergo corrosion if concentration of O2 over the metal surface is not uniform.
The portion at which O2 concentration is more acts as cathode and the portion at which the O2
concentration is less acts as anode. Hence the metal undergoes corrosion at points where O2 concentra-
tion is less.
E.g. When half portion of iron rod is immersed in NaCl solution, the immersed portion undergoes
corrosion due to less oxygenation.

Factors promoting corrosion

1) Nature of impurity: Corrosion is favored when the impurity is a more cathodic metal.
E.g. Cu is more cathodic than Zn and favors the corrosion of Zinc.
2) Concentration of O2: The portion of metal with less oxygen concentration favors corrosion.
E.g. When a half portion of iron rod is immersed in NaCl solution, the immersed portion
undergoes corrosion due to less oxygenation.
3) Highly conducting solutions favor rapid corrosion.

Prevention of corrosion
1) By avoiding the contact with surroundings by painting the surface of metal.
2) By adding another metal which is more anodic than the metal to prevent corrosion.
e.g. Zinc is more anodic than iron. Hence zinc is added to iron to prevent corrosion. This is
called galvanization.
3) By avoiding the contact of metal with other materials which are good electical conductors.

PASSIVITY
The state of non reactivity reached after an initial state of reactivity is called passivity.
Passivity of metals can be classified into
1) Chemical passivity
Electrochemistry 18
2) Mechanical passivity
3) Electrochemical passivity

1) Chemical passivity : This state is achieved by chemical reaction over metals.

E.g. Iron is attacked initially by conc.HNO3 and dissolves in it. But after sometime, the reactions is
stopped and iron becomes passive. At this stage iron cannot displace Ag from AgNO3 solution.

2) Mechanical passivity: An invisible thin film of oxide formed over metal surface prevent it from reacting
with acids. This is called mechanical passivity.
E.g. An invisible layer of PbO2 formed over the surface of Pb makes it passive and hence Pb is not
soluble in acids. This type of passivity is also shown by Fe, Co, Ni, Mn etc.,

3) Electrochemical passivity: During electrochemical processes, the dissolution of metal at anode is stopped
after some time. This is called electrochemical passivity.
E.g. Zn, Fe, Ni metals acting as anodes dissolve in the solution due to oxidation as follows.
Zn --------> Zn2+ + 2e-
Ni --------> Ni2+ + 2e-
But they stop dissolving after some time during electrochemical processes.

Theory of passivity
A metal becomes passive due to the formation of invisible thin film of its oxide over the surface which
prevents further reaction. Usually a thick layer of oxide is also formed beneath the thin film.
 IIT-JEE Review Questions
Halogens and their compounds
Level-1(Following Questions have only one correct response)

Q1. Which is the incorrect statement regarding halogens? (B)

(A) They are strong oxidizing agent and oxidizing power decreases down the group.
(B) They all disproportionate in aqueous alkali.
(C) Upper halogen in the group displaces lower halides from aqueous solution.
(D) Their boiling points increases from top to bottom in the group.
Q2. The wrong statement regarding hydrohalic acid is: (B)

(A) They are all strongly acidic and acid strength increases from HF to HI.
(B) They are all strong reducing agent and reducing power increases from HF to HI.
(C) HF is most soluble in water.
(D) HF attack glass.
Q3. Which of the following reaction/product is wrongly matched? (C)

(A) Cl2 + HgO Cl2O + HgCl2.HgO (B) NaClO3 + H2C2O4 ClO2 + CO2 + Na2C2O4
(C) ClO2 + NaOH NaClO3 + H2O (D) Cl2O6 + NaOH NaClO3 + NaClO4 + H2O
Q4. Which of the following statement regarding oxides of chlorine is not correct? (D)

(A) Cl2O is a symmetrical oxide. (B) ClO2 is a symmetrical oxide

(C) Cl2O6 has a ClCl bond (D) Cl2O7 has a ClCl bond.
Q5. Which of the following is incorrect statement regarding oxides of chlorine? (C)

(A) They are all acidic in aqueous solution. (B) They are all oxidizing agent.
(C) They are all pure anhydride. (D) Lower oxides are both oxidizing and reducing agent.
Q6. Which of the following is the correct order of acidic strength? A
(A) Cl2O7 > SO2 > P4O10 (B) CO2 > N2O5 > SO3
(C) Na2O > MgO > Al2O3 (D) K2O > CaO > MgO

Q7. Which of the following species are present in chlorine water? (D

(a) Only HCl (b) only HClO (c) HCl and HClO2 (d) HCl and HClO
Q8. Which of the following is called Euchlorine? (A)

(a) Cl2 + ClO2 (b) Cl2 + CO (c) CO2 + ClO2 (d) CO + ClO2
Q9. Chlorine can not be obtained by action of HCl on (C)

(a) KMnO4 (b) MnO2 (c) NaCl (d) K2Cr2O7

Q10. Chlorine may be prepared in the laboratory by the action of hydrochloric acid on (C)

(a) NaCl (b) MnSO4 (c) MnO2 (d) Na2SO4

1
Q11. Chlorine acts as a bleaching agent only in presence of (B)

(a) Dry air (b) Moisture (c) Sunlight (d) Pure oxygen
Q12. Which of the following can not act as a reducing agent under any conditions? (D)

(a) HI (b) KMnO4 (c) K2Cr2O7 (d) None of these

Q13. Which of the following is the strongest oxidizing agent? (A)

(a) HClO (b) HClO2 (c) HClO3 (d) HClO4

Q14. Predict the products if a reaction occurs when Cl2(g) and KF(aq) are mixed (C)

(a) KCl(aq) and KF(aq) (b) KCl(aq) and F2(g) (c) No reaction
(d) C/F and KCl /aq (e) K2 Cl2(s) and KCl(aq)
Q15. Bleaching powder on treatment with excess of HCl gives (D)

(a) CaO (b) CaO and Cl2 (c) CaCl2 (d) CaCl2 and Cl2
Q16. HI on reaction with H2SO4 yields (B)

(a) H2O2 & I2 (b) SO2 & I2 (c) HIO3 (d) No reaction
Q17. The least stable halogen acid is (D)

(a) HF (b) HCl (c) HBr (d) HI

Q18. Which of the following is the best reducing agent? (D)

(a) F (b) Cl (c) Br (d) I

Q19. When chlorine and CCl4 are added to a solution of an iodine and shaken, the colour obtained is (C)

(a) Brown (b) Orange (c) Violet (d) Yellow

Q20. Which of the following has the highest bond dissociation energy? (B)

(a) F2 (b) Cl2 (d) Br2 (d) I2

Q21. Which of the following absorbs yellow colour to undergo excitation of electrons? (D)

(a) F2 (b) Cl2 (d) Br2 (d) I2

Q22. Caliche is (A)

(a) NaNO3 + NaIO3 (b) NaIO3 (c) NaNO2 + NaIO3 (d) NaNO3 + I2
Q23. Which of the following is least soluble in water (C)

(a) Cl2 (b) Br2 (c) I2 (d) NaOH

Q24. Which of the following gives orange yellow colour with starch solution? (C)

(a) F2 (b) Cl2 (c) Br2 ((d) I2

Q25. Which of the following combines with all nonmetals directly except with N2 and O2? (A)

(a) F2 (b) Cl2 (c) Br2 (d) I2

Q26. Which of the following can turn starch iodide paper blue? (D)

(a) F2 (b) Cl2 (c) Br2 (d) All of these

Q27. The B.P. of hydrogen halides follows the order (D)

(a) HF > HCl > HBr > HI (b) HF > HI > HBr > HCl
(c) HCl > HBr > HF > HI (d) HF > HI > HCl > HBr
Q28. The decreasing order of acid strength for the hydrogen halides is (A)

(a) HI > HBr > HCl > HF (b) HF > HCl > HI > HBr
(c) HCl > HBr > HI > HF (d) HBr > HI > HCl > HF

2
Q29. Strongest reducing agent is (D)

(a) HF (b) HCl (c) HBr (d) HI

Q30. HF can reduce (D)

(a) H2SO4 (b) KMnO4 (c) K2Cr2O7 (d) None of these

Q31. Which one of the following is the most stable to heat? (A)

(a) HCl (b) HClO (c) HBr (c) HI

Q32. The most volatile compound among the following is (B)

(a) HI (b) HCl (c) HF (d) HBr

Q33. Oxidising strength of oxyacids of chlorine is (C)

(a) HClO4 > HClO3 > HClO2 > HClO (b) HClO4 > HClO2 > HClO3 > HClO
(c) HClO > HClO2 > HClO3 > HClO4 (d) HClO > HClO3 >HClO2 > HClO4
Q34. The thermal stability of oxy-acid of chlorine is (A)

(a) HClO4 > HClO3 > HClO2 > HClO (b) HClO4 > HClO2 > HClO3 > HClO
(c) HClO > HClO2 > HClO3 > HClO4 (d) HClO > HClO3 >HClO2 > HClO4
Q35. The strongest acidic oxyacid among the following is (D)

(a) HClO (b) HClO2 (c) HClO3 (d) HClO4

Q36. In the following strongest acid is (D)

(a) HF (b) HCl (c) HBr (d) HI

Q37. Which is the highest melting halide among the following? (B)

(a) NaCl (b) NaF (b) NaBr (d) NaI

Q38. Sea weekds are important source of (C)

(a) Iron (b) Chlorine (c) Iodine (d) Bromine

Q39. The solubility of iodine in water is increased by- (D)

(a) Boiling the solution (b) Cooling the solution

(c) Additing acid (d) Addition potassium iodide
Q40. HCl is added to the following reactions cant be used for the respective preparation? (A)

(a) BaO2 (b) MnO2 (c) PbO2 (d) NO2

Q41. Which amongst the following reactions cant be used for the respective preparation? (A)

(a) 2KBr + H2SO4 (conc) K2SO2 + 2HBr (b) NaCl + H2SO4(conc) NaHSO4 + HCl
(c) NaHSO4 + NaCl Na2SO4 + HCl (d) CaF2 + H2SO4 CaSO4 + 2HF
Q42. Which one of the following chlorides is not hydrolysed in water at room temperature to give hydrogen chloride? (B)

(a) aluminium chloride (b) calcium chloride (c) silicon tetrachloride (d) sulphur dichloride
Q43. In which of the following glass is soluble (D)

(a) HCl (b) HI (c) HBr (d) HF

Q44. Which of the following combination is most likely to form predominantly covalent bonds? (C)

(a) Sodium and hydrogen (b) Magnesium and oxygen

(c) bromine and fluorine (d) Cesium and fluorine
Q45. Which of the following has the lowest boiling point? (A)

(a) F2 (b) Cl2 (c) Br2 (d) I2

3
Q46. In the preparation of chlorine from HCl, MnO2 acts as (C)

(a) oxidizing agent (b) reduction agent (c) catalystic agent (d) dehydrating agent
Q47. Which of the following will displace the halogen from the solution of halide? (C)

(a) Cl2 added to NaF (b) Cl2 added to KCl (c) Br2 added to NaCl (d) Br2 added to NaI
Q48. Which of the following non-metal brings about highest oxidation state of metals? (C)

(a) I (b) O (c) F (d) Br

Q49. Bromine (molecular mass, 160 amu) boils at 59C, whereas iodine monochloride (molecular mass, 162 amu) boils at 92C. (C)
The best explanation for this difference in boiling points is
(a) the difference in molecular masses
(b) the I Cl bond is stronger than the Br Br bond
(c) Br2 is a non-polar molecular, ICI is polar
(d) The vander Waals forces in ICI are stronger than in Br2
Q50. Out of HBr, HCl and HI the decreasing order of reducing strength is (A)

(a) HI > HBr > HCl (b) HI > HCl > HBr (c) HCl > HBr > HI (d) HBr > HCl > HI
Q51. The purification of iodine is done by (C)

(a) Distillation (b) fractional crystallization (c) sublimation (d) steam distillation
Q52. Conc. H2SO4 cannot be used to prepare HBr from NaBr because it B
(A) reacts slowly with NaBr (B) oxidises HBr (C) reduces HBr (D) disproportionates HBr

Q53. An inorganic white crystalline compound (A) has a rock salt structure. (A) on reaction with cone. H2SO4 and MnO2, A
evolves a pungent smelling, greenish-yellow gas (B). Compound (A) gives white ppt. of (C) with AgNO3 solution.
Compounds (A), (B) and (C) will be respectively
(A) NaCl, Cl2, AgCl (B) NaBr, Br2, NaBr
(C) NaCl, Cl2, Ag2SO4 (D) Na2CO3, CO2, Ag2CO3

Q54. The correct order of acidic strength of oxy-acids of chlorine is A

(A) HClO < HClO2 < HClO3 < HClO4 (B) HClO4 < HClO3 < HClO2 < HClO
(C) HClO > HClO4 > HClO3 > HClO2 (D) HClO4 < HClO2 > HClO3 > HClO

Q55. When chlorine gas is passed through an aqueous solution of a potassium halide in the presence of chloroform, a violet D
colouration is obtained. On passing more of chlorine water, the violet colour is disappeared and solution becomes
colourless. This test confirms the presence of ........... in aqueous solution.
(A) chlorine (B) fluorine (C) bromine (D) iodine

Q56. Which is incorrectly matched? D

(A) CsBr3
Cs+ + Br3 (B) I4O9
I3+ + (IO3 )3
(C) AgBrO3
Ag+ + BrO3 (D) I2O4
IO2 + IO2+

Q57. SO2 reacts with Cl2 to form- (B)

(a) SOCl2 (b) SO2Cl2 (c) SCl2 (d) S2Cl2

Q58. Chorine acts as a bleaching agent only in the presence of (C)

(a) dry air (b) sunlight (c) moisture (d) pure oxygen
Q59. Br2 vapour turns, starch + KI paper (B)

(a) Brown (b) blue (d) red (d) violet

Q60. The oxide of chlorine which is colourless oily liquid is (D)

(a) Cl2O (b) Cl2O6 (c) ClO2 (d) Cl2O

4
Q61. The element which can displace three other halogens form their compounds is (D)

(a) Cl (b) Br (c) I (d) F

Q62. Which of the following oxides is the most acidic? (A)

(a) Cl2O5 (b) Cl2O3 (c) ClO2 (d) Cl2O

Q63. Tincture of iodine contains (C)

(a) I2, and rectified spirit (b) I2, and water

(c) I2, KI and rectified spirit (d) KI and retified spirit
Q64. Which chlorine is passed over dry slaked lime at room temperature, the main reaction product is (B)

(a) CaCl2 (b) CaOCl2 (c) Ca(ClO2)2 (d) Ca(OCl)2

Q65. In etching of the glass, the soluble product obtained is (C)

(a) H2SiO (b) H2SiF (c) H2SiF6 (d) SiF4

Q66. Although KBr can react with H2SO4 to produce HBr, syrupy H3PO4 is recommended for the preparation of HBr from (D)
KBr.Why?
(a) H2SO4 is more volatile than H3PO4 (b) H2SO4 is stronger than H3PO4
(c) H2SO4 is less reactive than H3PO4 (d) H2SO4 oxidises HBr to Br2 itself being reduced to SO2.
Q67. The most volatile acid is (B)

(a) HF (b) HCl (c) HBr (d) HI

Q68. Which reaction does not occur? (D)

(a) CuO + H2 Cu + H2O (b) Fe + H2SO4 FeSO4 + H2

(c) Cu + 2AgNO3 Cu(NO3)2 + Ag (d) 2KBr + I2 2KI + Br2

5
 Answers
1. (B) 21. (D) 41. (A) 61. (D)
2. (B) 22. (A) 42. (B) 62. (A)
3. (C) 23. (C) 43. (D) 63. (C)
4. (D) 24. (C) 44. (C) 64. (B)
5. (C) 25. (A) 45. (A) 65. (C)
6. (A) 26. (D) 46. (C) 66. (D)
7. (D 27. (D) 47. (C) 67. (B)
8. (A) 28. (A) 48. (C) 68. (D)
9. (C) 29. (D) 49. (C)
10. (C) 30. (D) 50. (A)
11. (B) 31. (A) 51. (C)
12. (D) 32. (B) 52. (B)
13. (A) 33. (C) 53. (A)
14. (C) 34. (A) 54. (A)
15. (D) 35. (D) 55. (D)
16. (B) 36. (D) 56. (D)
17. (D) 37. (B) 57. (B)
18. (D) 38. (C) 58. (C)
19. (C) 39. (D) 59. (B)
20. (B) 40. (A) 60. (D)

6
 IIT JEE-2008 (PAPER-2)
C. Question paper format:
14. The question paper consists of 3 parts (Part-I : Mathematics, Part-II : Physics, Part-III : Chemistry).
Each part has 4 sections.
15. Section I contains 9 multiple choice questions. Each question has 4 choices (A), (B), (C) and (D), out
of which only one is correct.
16. Section II contains 4 Reasoning type questions. Each question contains STATEMENT-1 and
STATEMENT-2.
Bubble (A) if both the statements are TRUE and STATEMENT-2 is the correct explanation of
STATEMENT-1.
Bubble (B) if both the statements are TRUE but STATEMENT-2 is NOT the correct explanation of
STATEMENT-1.
Bubble (C) if STATEMENT-1 is TRUE and STATEMENT-2 is FALSE
Bubble (D) if STATEMENT-1 is FALSE and STATEMENT-2 is TRUE
17. Section III contains 2 paragraphs. Based upon each paragraph, 3 multiple choice question have to be
answered. Each question has 4 choices (A), (B), (C) and (D), out of which only one is correct.
18. Section IV contains 3 questions. Each question contains statements given in 2 columns. Statements in
the first column have to be matched with statements in the second column. The answers to these questions
have to be appropriately bubbled in the ORS as per the instructions given at the beginning of the section.

D. Marking Scheme:
19. For each question in Section I, you will be awarded 3 marks if you have darkened only the bubble
corresponding to the correct answer and zero mark if no bubble is darkened. In all other cases, minus
one (1) mark will be awarded.
20. For each question in Section II, you will be awarded 3 marks if you have darkened all the bubble(s)
corresponding to the correct answer and zero mark if no bubble is darkened. In all other cases, minus
one (1) mark will be awarded.
21. For each question in Section III, you will be awarded 4 marks if you darken only the bubble
corresponding to the correct answer and zero mark if no bubble is darkened. In all other cases, minus
one (1) mark will be awarded.
22. For each question in Section IV, you will be awarded 6 marks if you darken ALL the bubbles
corresponding ONLY to the correct answer or awarded 1 mark each for correct bubbling of answer
in any row. No negative mark will be awarded for an incorrectly bubbled answer.

[1]
 IIT JEE-2008 PAPER-2

MATHEMATICS
PART I
SECTION - I
Straight Objective Type
This section contains 9 multiple choice questions. Each question has 4 choices (A), (B), (C) and (D), out
of which ONLY ONE is correct.
There is NEGATIVE marking. 1 mark will be deducted for wrong answer.
Q.1 Let
ex
e4x e2x 1 e 4x e 2x 1 dx
ex
I= dx , J =

Then, for an arbitrary constant C, the value of J I equals

1 e 4 x e 2 x 1 e2x ex 1
(B) 2 log 2 x +C
1
(A) 2 log 4 x +C
e e 1
2x x
e e 1

e2x ex 1 1 e 4 x e 2 x 1
(C) 2 log 2 x +C
1
(D) 2 log 4 x 2 x +C
e e 1
x
e e 1
Ans. [C]

Q.2 Let g (x) = log f (x) where f (x) is a twice differentiable positive function on (0, ) such that
f (x + 1) = x f (x). Then for N = 1, 2, 3
1 1
g' ' N g' ' =
2 2
1 1 1 1
(A) 41 ..... 4 1 .....
1 1
2 (B) 2
9 25 (2 N 1) 9 25 (2 N 1)

1 1 1 1
(C) 41 ..... (D) 41 .....
1 1

9 25 (2 N 1) 2 9 25 (2 N 1) 2
Ans. [A]

Q.3 Let two non-collinear unit vector a and b form an acute angle. A point P moves so that at any time t the
position vector O P (where O is the origin) is given by a cos t b sin t . When P is farthest from origin

O, let M be the length of O P and u be the unit vector along O P . Then,

a b a b
1 1

(A) u and M (1 a b) 2 (B) u and M (1 a b) 2

| a b | | a b |

a b a b
1 1

(C) u and M (1 2a b) 2 (D) u and M (1 2a b) 2

| a b | | a b |
Ans. [A]
[2]

Let the function g : ( , ) , be given by g (u) = 2 tan1(eu) . Then, g is
2 2
Q.4
2
(A) even and is strictly increasing in (0, )
(B) odd and is strictly decreasing in ( , )
(C) odd and is strictly increasing in ( , )
(D) neither even nor odd, but is strictly increasing in ( , )
Ans. [C]

Q.5 Consider a branch of the hyperbola

x2 2y2 2 2 x 4 2 y 6 = 0
with vertex at the point A. Let B be one of the end points of its latus rectum. If C is the focus of the
hyperbola nearest to the point A, then the area of the triangle ABC is

1 1
2 3 2 3
(A) 1 (B) (C) 1 (D)
3 2 3 2
Ans. [B]

Q.6 A particle P starts from the point z0 = 1 + 2i, where i = 1 . It moves first horizontally away from origin
by 5 units and then vertically away from origin by 3 units to reach a point z1. From z1 the particle moves

2 units in the direction of the vector i j and then it moves through an angle 2 in anticlockwise
direction on a circle with centre at origin, to reach a point z2. The point z2 is given by
(A) 6 + 7i (B) 7 + 6i (C) 7 + 6i (D) 6 + 7i
Ans. [D]

1 sin x 1 sin x
Q.7 The area of the region between the curves y = and y = bounded by the lines
cos x cos x

x = 0 and x = is
4
2 1 2 1

t 4t
(A) dt (B) dt
0 (1 t ) 1 t
2 2
0 (1 t ) 1 t
2 2

2 1 2 1

4t t
(C) dt (D) dt
0 (1 t 2 ) 1 t 2 0 (1 t 2 ) 1 t 2
Ans. [B]

Q.8 An experiment has 10 equally likely outcomes. Let A and B be two non-empty events of the experiment.
If A consists of 4 outcomes, the number of outcomes that B must have so that A and B are independent,
is
(A) 2, 4 or 8 (B) 3, 6, or 9 (C) 4 or 8 (D) 5 or 10
Ans. [D]

[3]
Q.9 Consider three points P = sin( ), cos , Q = cos( ), sin and
R = cos( ), sin( ) , where 0 < , , < /4
(A) P lies on the line segment RQ (B) Q lies on the line segment PR
(C) R lies on the line segment QP (D) P, Q, R are non collinear
Ans. [D]

SECTION-II
Reasoning Type
This section contains 4 reasoning type questions. Each question has 4 choices (A), (B), (C) and (D), out
of which ONLY ONE is correct.
There is NEGATIVE marking. 1 mark will be deducted for wrong answer.

Q.10 Suppose four distinct positive numbers a1, a2, a3, a4 are in G.P. Let b1 = a1, b2 = b1 + a2, b3 = b2 + a3
and b4 = b3 + a4.
STATEMENT-1 : The number b1, b2, b3, b4 are neither in A.P. nor in G.P.
and
STATEMENT-2 : The number b1, b2, b3, b4 are in H.P.
(A) STATEMENT-1 is True, STATEMENT-2 is True; STATEMENT-2 is a correct explanation for
STATEMENT-1
(B) STATEMENT-1 is True, STATEMENT-2 is True; STATEMENT-2 is NOT a correct explanation
for STATEMENT-1
(C) STATEMENT-1 is True, STATEMENT-2 is False
(D) STATEMENT-1 is False, STATEMENT-2 is True
Ans. [C]

Q.11 Consider
L1 : 2x + 3y + p 3 = 0
L2 : 2x + 3y + P + 3 = 0,
where p is a real number, and C : x2 + y2 + 6x 10y + 30 = 0.
STATEMENT-1 : If line L1 is a diameter of circle C, then line L2 is not always a diameter of circle C.
and
STATEMENT-2 : If line L1 is a diameter of circle C, then line L2 is not a chord of circle C.
(A) STATEMENT-1 is True, STATEMENT-2 is True; STATEMENT-2 is a correct explanation for
STATEMENT-1
(B) STATEMENT-1 is True, STATEMENT-2 is True; STATEMENT-2 is NOT a correct explanation
for STATEMENT-1
(C) STATEMENT-1 is True, STATEMENT-2 is False
(D) STATEMENT-1 is False, STATEMENT-2 is True
Ans. [C]

[4]
Q.12 Let a solution y = y (x) of the differential equation

x x 2 1 dy y y 2 1 dx 0
2
satisfy y (2) = .
3
1
STATEMENT-1 : y (x) = sec sec x
6
and

1 2
1 2 3 1
STATEMENT-2 : y (x) is given by
y x x
(A) STATEMENT-1 is True, STATEMENT-2 is True; STATEMENT-2 is a correct explanation for
STATEMENT-1
(B) STATEMENT-1 is True, STATEMENT-2 is True; STATEMENT-2 is NOT a correct explanation
for STATEMENT-1
(C) STATEMENT-1 is True, STATEMENT-2 is False
(D) STATEMENT-1 is False, STATEMENT-2 is True
Ans. [C]

1
Let a, b, c, p, q be real numbers. Suppose , are the roots of the equation x2 + 2px + q = 0 and a,

Q.13
are the roots of the equation ax2 + 2bx + c = 0, where 2 {1, 0, 1}
STATEMENT-1 : (p2 q)(b2 ac) 0
and
STATEMENT-2 : b pa or c qa
(A) STATEMENT-1 is True, STATEMENT-2 is True; STATEMENT-2 is a correct explanation for
STATEMENT-1
(B) STATEMENT-1 is True, STATEMENT-2 is True; STATEMENT-2 is NOT a correct explanation
for STATEMENT-1
(C) STATEMENT-1 is True, STATEMENT-2 is False
(D) STATEMENT-1 is False, STATEMENT-2 is True
Ans. [A]

[5]
 SECTION - III
Linked Comprehension Type
This section contains 3 paragraphs. Based upon each paragraph, 3 multiple choice questions have to be
answered. Each question has 4 choices (A), (B), (C) and (D), out of which ONLY ONE is correct.

There is NEGATIVE marking. 1 mark will be deducted for wrong answer.

Paragraph for Question Nos. 14 to 16
Consider the function f : ( , ) ( , ) defined by
x 2 ax 1
f (x ) ,0<a<2
x 2 ax 1

Q.14 Which of the following is true?

(A) (2 + a)2 f '' (1) + (2 a)2 f '' ( 1) = 0 (B) (2 a)2 f '' (1) (2 + a)2 f '' ( 1) = 0
(C) f ' (1) f ' (1) = (2 a)2 (D) f ' (1) f ' (1) = (2 + a)2
Ans. [A]

Q.15 Which of the following is true?

(A) f (x) is decreasing on (1, 1) and has a local minimum at x = 1
(B) f (x) is increasing on (1, 1) and has a local maximum at x = 1
(C) f (x) is increasing on (1, 1) but has neither a local maximum and nor a local minimum at x = 1.
(D) f (x) is decreasing on (1, 1) but has neither a local maximum and nor a local minimum at x = 1.
Ans. [A]
ex

1 t 2 dt
f ' (t )
Q.16 Let g (x) =
0
Which of the following is true?
(A) g ' (x) is positive on ( , 0) and negative on (0, )
(B) g ' (x) is negative on ( , 0) and positive on (0, )
(C) g ' (x) changes sign on both ( , 0) and (0, )
(D) g ' (x) does not change sign on ( , 0) and (0, )
Ans. [B]

Paragraph for Question Nos. 17 to 19

Consider the lines
x 1 y 2 z 1
L1 :
3 1 2
x 2 y 2 z3
L2 :
1 2 3

Q.17 The unit vector perpendicular to both L1 and L2 is

i 7 j 7 k i 7 j 5k i 7 j 5k 7i 7 j k
(A) (B) (C) (D)
99 5 3 5 3 99
Ans. [B]

[6]
Q.18 The shortest distance between L1 and L2 is
17 41 17
(A) 0 (B) (C) (D)
3 5 3 5 3
Ans. [D]

Q.19 The distance of the point (1, 1, 1) from the plane passing through the point (1, 2, 1) and whose
normal is perpendicular to both the lines L1 and L2 is
2 7 13 23
(A) (B) (C) (D)
75 75 75 75
Ans. [C]

SECTION - IV
MatrixMatch Type
This section contains 3 questions. Each question contains statements given in two columns which have to
be matched. Statements in Column I are labelled as A, B, C and D whereas
statements in Column II are labelled as P, Q, R and S. The answers to these questions have to be
appropriately bubbled as illustrated in the following example.
If the correct matches are A-P, A-S, B-Q, B-R, C-P, C-Q and D-S, then the correctly bubbled
4 4 matrix should be as follows: [6 Marks for correct (No Negative)]

Q.20 Consider the lines given by

L1 = x + 3y 5 = 0
L2 = 3x + ky 1 = 0
L3 = 5x + 2y 12 = 0
Match the statements / Expression in Column-I with the statements / Expressions in Column-II and
indicate your answer by darkening the appropriate bubbles in the 4 4 matrix given in OMR.

Column-I Column-II

(A) L1, L2, L3 are concurrent, if (P) k=9

6
(B) One of L1, L2, L3 is parallel to at least one of the other two, if (Q) k=
5

5
(C) L1, L2, L3 form a triangle, if (R) k=
6

(D) L1, L2, L3 do not form a triangle, if (S) k=5

Ans. (A)-S (B)-P,Q (C)-R (D)-P,Q,S

[7]
Q.21 Consider all possible permutations of the letters of the word ENDEANOEL
Match the statements / Expression in Column-I with the statements / Expressions in Column-II and
indicate your answer by darkening the appropriate bubbles in the 4 4 matrix given in OMR.

Column-I Column-II

(A) The number of permutations containing the word ENDEA is (P) 5!

(B) The number of permutations in which the letter E occurs in the (Q) 2 5!
first and the last position is

(C) The number of permutations in which none of the letters D, L, N (R) 7 5!

occurs in the last five positions is

(D) The number of permutations in which the letters A, E, O occurs (S) 21 5!

only in odd positions is
Ans. (A)-P (B)-S (C)-Q (D)-Q

Q.22 Match the statements / Expression in Column-I with the statements / Expressions in Column-II and
indicate your answer by darkening the appropriate bubbles in the 4 4 matrix given in OMR.

Column-I Column-II

x 2 2x 4
x2
(A) The minimum value of is (P) 0

(B) Let A and B be 3 3 matrices of real numbers, (Q) 1

(A + B)(A B) = (A B)(A + B). If (AB)t = (1)kAB, where (AB)t
is the transpose of the matrix AB, then the possible values of k are

a
(C) Let a = log3 log32. An integer k satisfying 1 < 2 ( k 3 )
< 2, must be (R) 2
less than

1
are
2
(D) If sin q = cos y, then the possible values of (S) 3

Ans. (A)-R (B)-Q,S (C)-R,S (D)-P,R

[8]
 PHYSICS
PART - II
SECTION - I
Straight Objective Type
This section contains 9 multiple choice questions. Each question has 4 choices (A), (B), (C) and (D), out
of which ONLY ONE is correct.

Q.23 A parallel plate capacitor C with plates of unit area and separation d is filled with a liquid of dielectric
d
constant K = 2. The level of liquid is initially. Suppose the liquid level decreases at a constant speed
3
V, the time constant as a function of time t is
Figure :

d d R
3

6 0 R (15d 9Vt ) 0 R
5d 3Vt 2d 2 3dVt 9V 2 t 2
(A) (B)

6 0 R (15d 9Vt ) 0 R
5d 3Vt 2d 2 3dVt 9V 2 t 2
(C) (D)
Ans. [A]

Q.24 A light beam is traveling from Region I to Region IV (Refer Figure). The refractive index in Regions I, II,
n0 n0 n0
III and IV are n0, , and , respectively. The angle of incidence for which the beam just
2 6 8
misses entering Region IV is
Figure :

Region I Region II Region III Region IV

n0 n0 n0
n0 6 8
2

0 0.2 m 0.6 m

3 1 1 1
(A) sin1 (B) sin1 (C) sin1 (D) sin1
4 8 4 3
Ans. [B]

[9]
Q.25 A vibrating string of certain length under a tension T resonates with a mode corresponding to the first
overtone (third harmonic) of an air column of length 75 cm inside a tube closed at one end. The string
also generates 4 beats per second when excited along with a tuning fork of frequency n. Now when the
tension of the string is slightly increased the number of beats reduces to 2 per second. Assuming the
velocity of sound in air to be 340 m/s, the frequency n of the tuning fork in Hz is :
(A) 344 (B) 336 (C) 117.3 (D) 109.3
Ans. [A]

Q.26 A radioactive sample S1 having an activity of 5Ci has twice the number of nuclei as another sample S2
which has an activity of 10Ci. The half lives of S1 and S2 can be :
(A) 20 years and 5 years, respectively (B) 20 years and 10 years, respectively
(C) 10 years each (D) 5 years each
Ans. [A]

Q.27 A transverse sinusoidal wave moves along a string in the positive x-direction at a speed of 10 cm/s. The
wavelength of the wave is 0.5 m and its amplitude is 10 cm. At a particular time t, the snap-shot of the
wave is shown in figure. The velocity of point P when its displacement is 5 cm is :
Figure :
y

3 3
(A) j m/s (B) j m/s
50 50

(D)
3 3
(C) i m/s i m/s
50 50
Ans. [A]

[10]
 q q 2q
Q.28 Consider a system of three charges , and placed at points A, B and C, respectively, as
3 3 3
shown in the figure. Take O to be the centre of the circle of radius R and angle CAB = 60
Figure :
y

C x
O
60

q
(A) The electric field at point O is 8 R 2 directed along the negative x-axis
0

(B) The potential energy of the system is zero

q2
54 0 R 2
(C) The magnitude of the force between the charges at C and B is

q
(D) The potential at point O is 12 R
0
Ans. [C]

Q.29 A block (B) is attached to two unstretched springs S1 and S2 with spring constants k and 4k, respectively
(see figure I). The other ends are attached to identical supports M1 and M2 not attached to the walls.
The springs and supports have negligible mass. There is no friction anywhere. The block B is displaced
towards wall 1 by a small distance x (figure II) and released. The block returns and moves a maximum
distance y towards wall 2. Displacements x and y are measured with respect to the equilibrium position
y
of the block B. The ratio is
x
Figure :
2 1
M2 S2 S1 M1 I
B
2 x 1
M2 S2 S1 M1 II
B
x
1 1
(A) 4 (B) 2 (C) (D)
2 4
Ans. [C]

[11]
Q.30 A glass tube of uniform internal radius (r) has a valve separating the two identical ends. Initially, the valve
is in a tightly closed position. End 1 has a hemispherical soap bubble of radius r. End 2 has sub-
hemispherical soap bubble as shown in figure. Just after opening the valve,
Figure :

2 1

(A) air from end 1 flows towards end 2. No change in the volume of the soap bubbles
(B) air from end 1 flows towards end 2. Volume of the soap bubble at end 1 decreases
(C) no change occurs
(D) air from end 2 flows towards end 1. Volume of the soap bubble at end 1 increases
Ans. [B]

Q.31 A bob of mass M is suspended by a massless string of length L. The horizontal velocity V at position A
is just sufficient to make it reach the point B. The angle at which the speed of the bob is half of that at
A, satisfies
Figure :
B

V
A
3 3
(A) = (B) << (C) << (D) <<
4 4 2 2 4 4
Ans. [D]

[12]
 SECTION - III
Reasoning Type
This section contains 4 reasoning type questions. Each question has 4 choices (A), (B), (C) and (D), out
of which ONLY ONE is correct.

Q.32 STATEMENT-1 : For an observer looking out through the window of a fast moving train, the nearby
objects appear to move in the opposite direction to the train, while the distant objects appear to be
stationary.
and

STATEMENT-2 : If the observer and the object are moving at velocities V1 and V2 respectively with

reference to a laboratory frame, the velocity of the object with respect to the observer is V2 V1 .
(A) STATEMENT-1 is True, STATEMENT-2 is True ; STATEMENT-2 is a correct explanation for
STATEMENT-1
(B) STATEMENT-1 is True, STATEMENT-2 is True ; STATEMENT-2 is NOT a correct explanation
for STATEMENT-1
(C) STATEMENT-1 is True, STATEMENT-2 is False
(D) STATEMENT-1 is False, STATEMENT-2 is True
Ans. [B]

Q.33 STATEMENT-1 : For practical, the earth is used as a reference at zero potential in electrical circuits.
and
STATEMENT-2 : The electrical potential of a sphere of radius R with charge Q uniformly distributed
Q
on the surface is given by 4 R .
0
(A) STATEMENT-1 is True, STATEMENT-2 is True ; STATEMENT-2 is a correct explanation for
STATEMENT-1
(B) STATEMENT-1 is True, STATEMENT-2 is True ; STATEMENT-2 is NOT a correct explanation
for STATEMENT-1
(C) STATEMENT-1 is True, STATEMENT-2 is False
(D) STATEMENT-1 is False, STATEMENT-2 is True
Ans. [B]

Q.34 STATEMENT-1 : The sensitivity of a moving coil galvanometer is increased by placing a suitable
magnetic material as a core inside the coil.
and
STATEMENT-2 : Soft iron has a high magnetic permeability and cannot be easily magnetized or
demagnetized.
(A) STATEMENT-1 is True, STATEMENT-2 is True ; STATEMENT-2 is a correct explanation for
STATEMENT-1
(B) STATEMENT-1 is True, STATEMENT-2 is True ; STATEMENT-2 is NOT a correct explanation
for STATEMENT-1
(C) STATEMENT-1 is True, STATEMENT-2 is False
(D) STATEMENT-1 is False, STATEMENT-2 is True
Ans. [C]

[13]
Q.35 STATEMENT-1 : It is easier to pull a heavy object that to push it on a level ground.
and
STATEMENT-2 : The magnitude of frictional force depends on the nature of the two surfaces in
contact.
(A) STATEMENT-1 is True, STATEMENT-2 is True ; STATEMENT-2 is a correct explanation for
STATEMENT-1
(B) STATEMENT-1 is True, STATEMENT-2 is True ; STATEMENT-2 is NOT a correct explanation
for STATEMENT-1
(C) STATEMENT-1 is True, STATEMENT-2 is False
(D) STATEMENT-1 is False, STATEMENT-2 is True
Ans. [B]

SECTION - III
Linked Comprehension Type
This section contains 2 paragraphs. Based upon each paragraph, 3 multiple choice questions have to be
answered. Each question has 4 choices (A), (B), (C) and (D), out of which ONLY ONE is correct.

Paragraph for Question Nos. 36 to 38

The nuclear charge (Ze) is non-uniformly distributed within a nucleus of radius R. The charge density (r)
[charge per unit volume] is dependent only on the radial distance r from the centre of the nucleus as
shown in figure. The electric field is only along the radial direction.
Figure :

(r)

a r
R

Q.36 The electric field at r = R is :

(A) independent of a (B) directly proportional to a
(C) directly proportional to a2 (D) inversely proportional to a
Ans. [A]

Q.37 For a = 0, the value of d (maximum value of as shown in the figure) is :

3Ze 3Ze 4 Ze Ze
4R 3 R 3 3R 3 3R 3
(A) (B) (C) (D)
Ans. [B]

Q.38 The electric field within the nucleus is generally observed to be linearly dependent on r. This implies
R 2R
(A) a = 0 (B) a = (C) a = R (D) a =
2 3
Ans. [C]

[14]
 Paragraph for Question Nos. 39 to 41

A uniform thin cylindrical disk of mass M and radius R is attached to two identical massless springs of
spring constant k which are fixed to the wall as shown in the figure. The springs are attached to the axle
of the disk symmetrically on either side at a distance d from its centre. The axle is massless and both the
springs and the axle are in a horizontal plane. The unstretched length of each spring is L. The disk is
initially at its equilibrium position with its centre of mass (CM) at a distance L from the wall. The disk rolls

without slipping with velocity V0 V0 i . The coefficient of friction is .
Figure :

2d

d d

R V0

Q.39 The net external force acting on the disk when its centre of mass is at displacement x with respect to its
equilibrium position is :
2kx 4kx
(A) kx (B) 2kx (C) (D)
3 3
Ans. [D]

Q.40 The centre of mass of the disk undergoes simple harmonic motion with angular frequency equal to :
k 2k 2k 4k
(A) (B) (C) (D)
M M 3M 3M
Ans. [D]

Q.41 The maximum value of V0 for which the disk will roll without slipping is :
M M 3M 5M
(A) g (B) g (C) g (D) g
k 2k k 2k
Ans. [C]

[15]
 SECTION - IV
MatrixMatch Type

This section contains 3 questions. Each question contains statements given in two columns which have to
be matched. Statements in Column I are labelled as A, B, C and D whereas statements in Column II.
are labelled as p, q, r and s. The answers to these questions have to be appropriately bubbled as
illustrated in the following example.
If the correct matches are A-q, A-r, B-p, B-s, C-r, and D-q, then the correctly bubbled
4 4 matrix should be as follows:
p q r s
A p q r s
B p q r s
C p q r s
D p q r s

Q.42. Column I gives a list of possible set of parameters measured in some experiments. The variations of the
parameters in the form of graphs are shown in Column II. Match the set of parameters given in Column
I with the graphs given in Column II. Indicate your answer by darkening the appropriate bubbles of the
4 4 matrix given in the ORS.

Column I Column II
y

(A) Potential energy of a simple pendulum (y axis) (p)

as a function of displacement (x axis)
x
O
y

(B) Displacement (y axis) as a function of time (q)

(x axis) for a one dimensional motion at zero or
constant acceleration when the body is moving
x
along the positive x-direction. O

(C) Range of a projectile (y axis) as a function of its (r)

velocity (x axis) when projected at a fixed angle.

x
O
y

(D) The square of the time period (y axis) of a simple (s)

pendulum as a function of its length (x axis)

Ans. [(A) p (B) q, s (C) s (D) q] x

O

[16]
Q.43. Column I contains a list of processes involving expansion of an ideal gas. Match this with Column II.
describing the thermodynamic change during this process. Indicate your answer by darkening the
appropriate bubbles of the 4 4 matrix given in the ORS.

Column I Column II

(A) An insulated container has two chambers (p) The temperature of the gas
separated by a valve. Chamber I contains an decreases
ideal gas and the chamber II has vacuum. The
valve.

I II

ideal gas vacuum

(B) An ideal monoatomic gas expands to twice its (q) The temperature of the gas
original volume such that its original volume such increases or remains constant
1
that its pressure P , where V is the
V2
volume of the gas.

(C) An ideal monoatomic gas expands to twice its (r) The gas loses heat
1
original volume such that its pressure P ,
V4 / 3
where V is its volume.

(D) An ideal monoatomic gas expands such that its (s) The gas gains heat
pressure P and volume V follows the behaviour
shown in the graph.

V
V1 2V1

Ans. [(A) q (B) p, r (C) p, s (D) q, s]

[17]
Q.44. An optical component and an object S placed along its optic axis are given in Column I. The distance
between the object and the component can be varied. The properties of images are given in Column II.
Match all the properties of images from Column II with the appropriate components given in Column
I Indicate your answer by darkening the appropriate bubbles of the 4 4 matrix given in the ORS.

Column I Column II

S
(A) (p) Real image

S
(B) (q) Virtual image

S
(C) (r) Magnified image

S
(D) (s) Image at infinite

Ans. [(A) p, q, r, s (B) q, (C) p, q, r, s (D) p, q, r, s]

[18]
 CHEMISTRY
PART-III
SECTION-I
Straight Objective Type
This section contains 9 multiple choice questions. Each question has 4 choices (A), (B), (C) and (D), out
of which ONLY ONE is correct.

Q.45 Among the following, the surfactant that will from micelles in aqueous solution at the lowest molar
concentration at ambient conditions is
(A) CH3(CH2)15N+(CH3)3Br (B) CH3(CH2)11OSO3Na+
(C) CH3(CH2)6COONa+ (D) CH3(CH2)11N+(CH3)3Br
Ans. [A]

Q.46 Solubility product constants (Ksp) of salts of types MX, MX2 and M3X at temperature T are
4.0 108, 3.2 1014 and 2.7 1015, respectively. Solubilities (mol dm3) of the salts at temperature
T are in the order
(A) MX > MX2 > M3X (B) M3X > MX2 > MX
(C) MX2 > M3X > MX (D) MX > M3X > MX2
Ans. [D]

Q.47 Electrolysis of dilute aqueous NaCl solution was carried out by passing 10 milli ampere current. The time
required to liberate 0.01 mol of H2 gas at the cathode is (1 Faraday = 96500 C mol1)
(A) 9.65 104 sec (B) 19.3 104 sec (C) 28.95 104 sec (D) 38.6 104 sec
Ans. [B]

Q.48 Cellulose upon acetylation with excess acetic anhydride / H2SO4 (catalytic) gives cellulose triacetate
whose structure is
AcO
H O O
AcO H
(A) OAc H
H O O H
AcO H
OAc H H OAc
O O
H H H
OAc H H OAc
O H
H OAc
AcO
H O O
AcO H
OH H
H O O H
AcO H
OH H H OH
O O
(B) H H H
OH H H OH
O H
H OH
[19]
 AcO AcO AcO
O H O H
(C) H H H
H
H O O
H
OAc H OAc H
O O O
OAc H
H
H OAc H OAc H OAc

AcO AcO AcO

O H O H
H H H
H
H O O
(D) H
H H H
O
H H H
O O H
OAc OAc OAc OAc OAc OAc
Ans. [A]

Q.49 In the following reaction sequence, the correct structures of E, F and G are
O O
|| || I2
Heat [E] [F] + [G]
Ph * OH NaOH
(* implies 13C labelled carbon)
O O
|| ||
(A) E = * F= - + G = CHI3
Ph CH3 Ph * O Na
O O
|| ||
(B) E = * F= - + G = CHI3
Ph CH 3
Ph O Na
O O
|| || *
(C) E = * F= - + G = CHI
Ph CH 3
Ph O Na
3

O O
|| || *
(D) E = * F= - + G = CH 3I
Ph CH 3
Ph O Na
Ans. [C]

Q.50 The correct stability order for the following species is

+
+ +

O O +

(I) (II) (III) (IV)

(A) (II) > (IV) > (I) > (III) (B) (I) > (II) > (III) > (IV)
(C) (II) > (I) > (IV) > (III) (D) (I) > (III) > (II) > (IV)
Ans. [D]

[20]
Q.51 Among the following, the coloured compound is
(A) CuCl (B) K3 [Cu (CN)4] (C) CuF2 (D) [Cu(CH3CN)4] BF4
Ans. [C]

Q.52 The IUPAC name of [Ni(NH3)4] [NiCl4] is

(A) Tetrachloronickel (II)-tetraamminenickel (II)
(B) Tetraamminenickel (II)-tetrachloronickel (II)
(C) Tetraamminenickel (II)-tetrachloronickelate (II)
(D) Tetrachloronickel (II)-tetraamminenickelate (0)
Ans. [C]

Q.53 Both [Ni(CO)4] and [Ni(CN)4]2 are diamagnetic. The hybridisations of nickel in these complexes,
respectively, are
(A) sp3, sp3 (B) sp3, dsp2 (C) dsp2, sp3 (D) dsp2, dsp2
Ans. [B]

SECTION-II
Reasoning Type
This section contains 4 reasoning type questions. Each question has 4 choices (A), (B), (C) and (D), out
of which ONLY ONE is correct.

Q.54 STATEMENT-1 : Aniline on reaction with NaNO2 / HCl at 0C followed by coupling with -naphthol
gives a dark blue coloured precipitate.
and
STATEMENT-2 : The colour of the compound formed in the reaction of aniline with NaNO2 / HCl at 0
followed by coupling with -naphthol is due to the extended conjugation.
(A) STATEMENT-1 is True, STATEMENT-2 is True ; STATEMENT-2 is a correct explanation for
STATEMENT-1
(B) STATEMENT-1 is True, STATEMENT-2 is True ; STATEMENT-2 is NOT a correct explanation
for STATEMENT-1
(C) STATEMENT-1 is True, STATEMENT-2 is False
(D) STATEMENT-1 is False, STATEMENT-2 is True
Ans. [D]

Q.55 STATEMENT-1 : The geometrical isomers of the complex [M(NH3)4Cl2] are optically inactive.
and
STATEMENT-2 : Both geometrical isomers of the complex [M(NH3)4Cl2] possess axis of symmetry.
(A) STATEMENT-1 is True, STATEMENT-2 is True ; STATEMENT-2 is a correct explanation for
STATEMENT-1
(B) STATEMENT-1 is True, STATEMENT-2 is True ; STATEMENT-2 is NOT a correct explanation
for STATEMENT-1
(C) STATEMENT-1 is True, STATEMENT-2 is False
(D) STATEMENT-1 is False, STATEMENT-2 is True
Ans. [A]

[21]
Q.56 STATEMENT-1 : There is a natural asymmetry between converting work to heat and converting heat to
work.
and
STATEMENT-2 : No process is possible in which the sole result is the absorption of heat from a
reservoir and its complete conversion into work.
(A) STATEMENT-1 is True, STATEMENT-2 is True ; STATEMENT-2 is a correct explanation for
STATEMENT-1
(B) STATEMENT-1 is True, STATEMENT-2 is True ; STATEMENT-2 is NOT a correct explanation
for STATEMENT-1
(C) STATEMENT-1 is True, STATEMENT-2 is False
(D) STATEMENT-1 is False, STATEMENT-2 is True
Ans. [A]

Q.57 STATEMENT-1 : [Fe(H2O)5NO]SO4 is paramagnetic

and
STATEMENT-2 : The Fe in [Fe(H2O)5NO]SO4 has three unpaired electrons.
(A) STATEMENT-1 is True, STATEMENT-2 is True ; STATEMENT-2 is a correct explanation for
STATEMENT-1
(B) STATEMENT-1 is True, STATEMENT-2 is True ; STATEMENT-2 is NOT a correct explanation
for STATEMENT-1
(C) STATEMENT-1 is True, STATEMENT-2 is False
(D) STATEMENT-1 is False, STATEMENT-2 is True
Ans. [A]

SECTION-III
Linked Comprehension Type

Paragraph for Question No. 58 to 60

A tertiary alcohol H upon acid catalysed dehydration gives a product I. Ozonolysis of I leads to compounds
J and K. Compound J upon reaction with KOH gives benzyl alcohol and a compound L, whereas K on
reaction with KOH gives only M.
O
H 3C
Ph
M=
Ph H

Q.58 Compound H is formed by the reaction of

O O
|| ||
(A) + PhMgBr (B) + PhCH2MgBr
Ph CH3 Ph CH3

O O Me
(C) || + PhCH2MgBr (D) || +
Ph H Ph H Ph MgBr
Ans. [B]

[22]
Q.59 The structure of compound I is
Ph CH3 H3C Ph CH3 H3C CH3
Ph
(A) (B) (C) (D)
H Ph H Ph H CH2Ph Ph H
Ans. [A]

Q.60 The structures of compounds J, K and L, respectively, are

(A) PhCOCH3, PhCH2COCH3 and PhCH2COOK+
(B) PhCHO, PhCH2CHO and PhCOOK+
(C) PhCOCH3, PhCH2CHO and CH3COOK+
(D) PhCHO, PhCOCH3 and PhCOOK+
Ans. [D]

Paragraph for Question No. 61 to 63

In hexagonal systems of crystals, a frequently encountered arrangement of atoms is described as a

hexagonal prism. Here, the top and bottom of the cell are regular hexagons and three atoms are sandwiched
in between them. A space-filling model of this structure, called hexagonal close-packed (HCP), is
constituted of a sphere on a flat surface surrounded in the same plane by six identical spheres as closely
as possible. Three spheres are then placed over the first layer so that they touch each other and represent
the second layer. Each one of these three spheres touches three spheres of the bottom layer. Finally, the
second layer is covered with a third layer that is identical to the bottom layer in relative position. Assume
radius of every sphere to be r.

Q.61 The number of atoms in this HCP unit cells is

(A) 4 (B) 6 (C) 12 (D) 17
Ans. [B]

Q.62 The volume of this HCP unit cell is

64 3
(A) 24 2 r 3 (B) 16 2 r 3 (C) 12 2 r 3 (D) r
3 3
Ans. [A]

Q.63 The empty space in this HCP unit cell is

(A) 74% (B) 47.6 % (C) 32% (D) 26%
Ans. [D]

[23]
 SECTION-IV
Matrix Match Type

This section contains 3 questions. Each question contains statements given in two columns which have to
be matched. Statements in Column I are labelled as A, B, C and D whereas statements in Column II
are labelled as p, q, r and s. The answers to these questions have to be appropriately bubbled as
illustrated in the following example.
If the correct matches are A-q, A-r, B-p, B-s, C-r, C-s and D-q, then the correctly bubbled
matrix will look like the following :
p q r s
A p q r s
B p q r s
C p q r s
D p q r s

Q.64 Match the compounds in Column I with their characteristic test(s)/reaction(s) given in Column II.
Indicate your answer by darkening the appropriate bubbles of the 4 4 matrix given in the ORS.

Column I Column II
-
(A) H2N NH3Cl
+
(p) sodium fusion extract of the compound gives
Prussian blue colour with FeSO4
+ -
NH3I
(B) HO (q) gives positive FeCl3 test
COOH
+ -
(C) HO NH3Cl (r) gives white precipitate with AgNO3

-
NH NH3Br
+
(D) O2N (s) reacts with aldehydes to form the corresponding
hydrazone derivative
NO2

Ans. [(A) r,s (B) p,q (C) p,q,r (D) p,s]

[24]
Q.65 Match the entries in Column I with the correctly related quantum number(s) in Column II. Indicate
your answer by darkening the appropriate bubbles of the 4 4 matrix given in the ORS.

Column I Column II
(A) Orbital angular momentum of the (p) Principal quantum number
electron in a hydrogen-like atomic orbital

(B) A hydrogen-like one-electron wave (q) Azimuthal quantum number

function obeying Pauli principle

(C) Shape, size and orientation of hydrogen (r) Magnetic quantum number
like atomic orbitals

(D) Probability density of electron at the nucleus (s) Electron spin quantum number
in hydrogen-like atom

Ans. [(A) q, (B) p, q, r (C) p, q, r (D) p, q]

Q.66 Match the conversions in Column I with the type(s) of reaction(s) given in Column II. Indicate your
answer by darkening the appropriate bubbles of the 4 4 matrix given in the ORS.

Column I Column II

(A) PbS PbO (p) roasting

(B) CaCO3 CaO (q) calcination

(C) ZnS Zn (r) carbon reduction

(D) Cu2S Cu (s) self reduction

Ans. [A p, Bq, Cp, r, Dp, s ]

[25]
 IITJEE2004 Mains Paper

Chemistry
Time: 2 hours

Note: Question number 1 to 10 carries 2 marks each and 11 to 20 carries 4 marks each.

1. For the given reaction

A + B Products
Following data were given
Initial conc. (m/L). Initial conc. (m/L) Initial rate [mL-1s-1 ]
[A] [B]
0.1 0.1 0.05
0.2 0.1 0.1
0.1 0.2 0.05
a) Write the rate equation.
b) Calculate the rate constant.

Sol. a) Let the order w.r.t A & B are x any y respectively

r = K[A]x [B]y
0.05 = K[0.1]x [0.1]y
0.1 = K[0.2]x [0.1]y
or 2 = [2]x
x =1
0.05 = K[0.1]x [0.1]y
0.05 = K[0.1]x [0.2]y
1 = [2]y
y=0
b) rate equation = r = K[A] [B]0
0.1 = K[0.2]
K = 0.5 Sec-1

2. 100 ml of a liquid contained in an isolated container at a pressure of 1 bar. The pressure is steeply increased
to 100 bar. The volume of the liquid is decreased by 1 ml at this constant pressure. Find the H & U.

Sol. H =0, qp = U-W

W = PdV
= 1001 atmmL
= 10-2 KJ = U

3. Draw the shape of XeF4 and OSF4according to VSEPR theory. Show the lone pair of electrons on the
central atom

Sol. F
F F O
Xe
(square planar) F S (Trigonal bipyramidal)
F F (sp3d2) (sp3d)
F
F

1
 IIT-JEE 2004-M-2

4. The structure of D-Glucose is as follows

CHO a) Draw the structure of L Glucose.
b) Give the reaction of L Glucose with Tollens reagent.
H OH

HO H

H OH

H OH

HO

Sol. -
O O
CHO

H OH H OH

HO H +
HO H

Ag( NH3 )2

H OH H OH

HO H HO H
(L glu cos e)

HO HO

5. a) Draw New mann`s projection for the less stable staggered form of butane.
b) Relatively less stability of the staggered form is due to
i) Torsional strain.
ii) Vander Waals strain.
iii) Combination of the above two.
Sol. a) CH3
H CH3
. .

. H
H

H
b) Less stability is due to Vander Waals strain

6. Arrange the following oxides in the increasing order of Bronsted basicity.

Cl2 O7 , BaO, SO3 , CO 2 , B2 O3
Sol. Cl2 O7 < SO3 < CO 2 < B2 O3 < BaO

7. AlF3 is insoluble in anhydrous HF but when little KF is added to the compound it becomes soluble. On
addition of BF3 ,AlF3 is precipitated. Write the balanced chemical equations.

Sol. 3KF + AlF3 K3AlF6

K3AlF6 + 3BF3 AlF3 + 3KBF4

8. The crystal AB (rock salt structure) has molecular weight 6.023 y amu. where y is an arbitrary number in
amu.. If the minimum distance between cation & anion is y1/ 3 nm and the observed density is 20 Kg / m3 .
Find the
a) density in Kg / m3 and
b) type of defect

2
 IIT-JEE 2004-M-3

4 6.023 y
Sol. a) Density = [Since a = 2y1/3]
6.023 1023 8 y 1027
= 5 103 g / m 3
= 5Kg / m 3
b) Since the (density) calculated < density observed, it means the defect is metal excess defect.

9. Which of the following is more acidic and why?

+ +
NH3 NH3

Sol. + is more acidic due to inductive effect of fluorine

NH3

10. 7-bromo-1,3,5-cycloheptatriene exists as ionic species in aqueous solution while 5-bromo-1,3

cyclopentadiene doesnt ionise even in presence of Ag + (aq), Explain.

Sol. Br

Ag aq.

Aromatic Ion
(highly stable)

Ag

Br Antiaromatic Ion
(highly unstable)

11. a) The schrodinger wave equation for hydrogen atoms is

3/ 2
1
1 r r / a
2s = 1/ 2 2 e
4(2) a 0 a0
Where a0 is Bohrs radius. Let the radial node in 2s be at r0. Then find r in terms of a0.
b) A base ball having mass 100 g moves with velocity 100 m/sec. Find out the value of wave length of
base ball.
7
c) 92 X 234
6
Y. Find out atomic number, mass number of Y and identify it.

Sol. a) 22s = probability of finding electrons at any place

2= 0 at node

3
 IIT-JEE 2004-M-4

2
1 1 1
3
r r / a
=0= 2 e 0
2

4 2 a 0 a0
r r
2 = 0 2 = 2a0 = r
a0 a0
h 6.626 1034
b) = =
mv 100 103 100
= 6.62610-35 m = 6.62610-25 A
c) Yis 84Po206

12. On the basis of ground state electronic configuration arrange the following molecules in increasing O-O
bond length order.
KO2, O2, O2[AsF6].

2p y 2p y
2 1

Sol. O 2 = 1s 2 , 1s 2 , 2s 2 , 2s 2 , 2p 2x

2p z 2p z
2 1

10 6
bond order = =2
2
2P 2 2Py
* 2

O 2 = 1s2 , * 1s2 , 2s2 , * 2s2 , 2P 2 2Pzy2 * 2P 1 in [KO 2 ]

x
z
10 7 3
bond order = =
2 2

O +2
2P 2
= 1s2 , * 1s2 , 2s2 , * 2s2 , 2Px2 2Pzy2 * 2p y1

{ }
in [O 2 (AsF6 )]

10 5 5
bond order =
2 2
Bond length order is O2+ < O2 < O2

13. a) In the following equilibrium

N2O4(g) 2NO2(g)
when 5 moles of each are taken, the temperature is kept at 298 K the total pressure was found to be 20
bar. Given that
G 0f (N 2 O 4 ) = 100KJ
G 0f (NO 2 ) = 50KJ
i) Find G of the reaction
ii) The direction of the reaction in which the equilibrium shifts
b) A graph is plotted for a real gas which follows Vander Waals equation with PVm taken on Y axis &
P on X axis. Find the intercept of the line where Vm is molar volume
Sol. a) i) N2O4(g) 2NO2(g)
2
PNO 100
Reaction quotient = 2
= = 10 atm
PN O 10
2 4

G reaction = 2G f ( NO 2 ) G f ( N 2 O 4 )
0 = 100 100
G = G + RT lnk
G = RT ln Q
= 2.303 .082 298 log 9.9 = 56.0304 Lit atm. = Positive

4
 IIT-JEE 2004-M-5

ii) Therefore reaction will shift towards backward direction.

a
b) P + 2 (v m b) = RT
vm
aP 2 PV
P +
2
b = RT
( PV ) P

[PV)2 P+aP2][(PV) b)] = P(PV)2RT
P[(PV)2 + aP] (PV-bP)=P(PV)2RT
Put P = 0
(PV)3 = (PV)2 RT
Intercept = RT

14. a) 1.22 g C6H5 COOH is added into two solvent and data of Tb and Kb are given as:-
i) In 100 g CH3COCH3 Tb= 0.17
Kb = 1.7 Kg Kelvin /mol
ii) In 100 g benzene, Tb = 0.13 and Kb = 2.6 Kg Kelvin/mol
Find out the molecular weight of C6H5COOH in both the cases and interpret the result.
b) 0.1 M of HA is titrated with 0.1 M NaOH, calculate the pH at end point. Given Ka(HA)=510-6 and
<< 1
Sol. a) In first case
i) Tb = Kbm
1.22
0.17 = 1.7 M = 122
M 100 10 3
ii) In second case
Tb = Kbm
1.22
0.13 = 2.6
M 100 103
M = 244
Benzoic acid dimerises in benzene
0.1
b) Since at end point molarity of salt = = M
2
pH of salt of weak acid and strong base
( pK w + pK a + logc ) 1
pH = = [14 + 5.3010 + [-1.3010] pH = 9.
2 2
15. NO2 NO2

in not more than four steps. Also mention the temp and reaction
Convert
to
condition.

OH

Sol. NO2 NO2 NO2 NO2

NO2

Conc.H 2 SO 4

NH 4 HS

NaNO2 / HCl

H2 O

0 C 5 C

NO2 NH2 + OH
N
NCl
Cl
16.

+

KCN
DMF
(A)
C2 H5 ONa / C 2 H 5 OH
C6 H5 CHO /
(B)
H3 O

(C)
SOCl2
CH3 NH 2
(D)

Identify A to D.

5
 IIT-JEE 2004-M-6

CN
Sol. NC Ph

H
A= B=

O NH
COOH CH3

Ph Ph

C= D=

17. A1 & A2 are two ores of metal M. A1 on calcination gives black precipitate, CO2 & water.
n Black solid + CO2 + H2O
atio
l ci n
Ca

A1 dil HCl

KI I 2 + ppt

A 2
roasting
Metal + gas
K 2 Cr2 O7 + H 2SO4

green colour
Sol. A1 = Cu(OH) 2 CuCO3
A 2 = Cu 2S
Cu(OH) 2 CuCO 3
Calcination
2CuO + CO 2 + H 2 O
(A1) (Black Solid)

Cu(OH) 2 CuCO3 CuCl 2 + CO 2 + 3H 2 O

dilHCl

2CuCl2 + 4KI Cu 2 l2 + I 2 + 4KCl

2Cu 2S + 3O 2 2Cu 2 O + 2SO 2
( A2 )
Cu 2S + 2Cu 2 O 6Cu + SO 2
18. NiCl2 in the presence of dimethyl glyoxime (DMG) gives a complex which precipitates in the presence of
NH 4 OH , giving a bright red colour.
a) Draw its structure & show H-bonding
b) Give oxidation state of Ni & its hybridisation.
c) Predict wether it is paramagnetic or diamagnetic.
Sol. H3C N HO N
O CH3
C C

Ni

C C
N
H3C N CH3
OH O
Oxidation state of nickel is +2 and hybridization is dsp2
s = n(n + 2) B.M
n=0
s = 0

6
 IIT-JEE 2004-M-7

19. Find the equilibrium constant for the reaction

Cu+2 + In+2 Cu+ + In+3
Given that
E Cu +2 / Cu + = 0.15V
E In +2 / In + = 0.4V
E In +3 / In + = 0.42 V

Sol. Cu+2 +e- Cu+ G10 = - 0.15 F

In+2 + e- In+ + G20 = +0.4 F
In+ In+3 + 2 e- G30 = - 0.84 F
Cu+2 + In+2 Cu+ + In+3 G0 = - 0.59 F
- nFE = - 0.59F
E0cell F = 0.59F
E0Cell = 0.59
0.0591
Ecell = E - log K c
n
0.0591
0.59 = log Kc
1
Kc = 1010

20. An organic compound P having the molecular formula C5H10O treated with dil H2SO4 gives two
compounds, Q & R both gives positive iodoform test. The reaction of C5H10O with dil H2SO4 gives
reaction 1015 times faster then ethylene. Identify organic compound of Q & R. Give the reason for the extra
stability of P.

Sol. CH3

C5 H10 O is
H2C O CH3

CH3 CH3 CH3

+
C
H+

H 2O
+ C2 H 5OH
H2C O CH3 H3C O CH3 H3C O
Highly stable carbocation
P is stabilized by resonance

7
 ANEESH DAMODARAN

ANSWER: C

ANSWER: B

ANSWER: D
ANSWER: A

ANSWER: D
ANSWER: A

ANSWER: B

ANSWER: C
 ANSWER: B

ANSWER: A and C

ANSWER: B and D

ANSWER: A and B
ANSWER: C and D

ANSWER: A

ANSWER: D
ANSWER: C

ANSWER: B

ANSWER: C
ANSWER: 2

ANSWER: 5

ANSWER: 1

ANSWER: 4
 ANSWER: 3

ANSWER: either 0 or 8

ANSWER: 3

ANSWER: 3

ANSWER: 0

ANSWER: 4
ANSWER: D

ANSWER: C

ANSWER: C

ANSWER: A
 ANSWER: A

ANSWER: B

ANSWER: B

ANSWER: D
 ANSWER: C and D

ANSWER: B

ANSWER: A and C and D

ANSWER: B and C

ANSWER: A

ANSWER: D

ANSWER: C
ANSWER: D

ANSWER: B

ANSWER: A

ANSWER: 3
ANSWER: 2

ANSWER: 5

ANSWER: 2

ANSWER: 6

ANSWER: 4

ANSWER: 1
ANSWER: 3

ANSWER: 3

ANSWER: 9
ANSWER: C

ANSWER: D

ANSWER: D
ANSWER: C

ANSWER: B
ANSWER: C

ANSWER: A
 ANSWER: A

ANSWER: A and D

ANSWER: A and C
.
 ANSWER: A and C

ANSWER: A and B and C

ANSWER: A and B and C and D

ANSWER: B or C or (B and C)
Option C implies option B.

ANSWER: B

ANSWER: D
ANSWER: A

ANSWER: B
ANSWER: 6

ANSWER: 3

ANSWER: 4

ANSWER: 9

ANSWER: 5
 ANSWER: 4

ANSWER: 6

ANSWER: 3

ANSWER: 8

ANSWER: 7
********************************************
 FIITJEE Solutions to
IITJEE-2007
(Paper-I, Code-7)
Time: 3 hours M. Marks: 243

Note: (i) The question paper consists of 3 parts (Physics, Chemistry and Mathematics). Each part has 4 sections.
(ii) Section I contains 9 multiple choice questions which have only one correct answer. Each question carries +3 marks
each for correct answer and 1 mark for each wrong answer.
(iii) Section II contains 4 questions. Each question contains STATEMENT-1 (Assertion) and STATEMENT-2 (Reason).
Bubble (A) if both the statements are TRUE and STATEMENT-2 is the correct explanation of STATEMENT-1
Bubble (B) if both the statements are TRUE but STATEMENT-2 is NOT the correct explanation of STATEMENT- 1
Bubble (C) if STATEMENT-1 is TRUE and STATEMENT-2 is FALSE.
Bubble (D) if STATEMENT-1 is FALSE and STATEMENT-2 is TRUE.
carries +3 marks each for correct answer and 1 mark for each wrong answer.
(iv) Section III contains 2 paragraphs. Based upon each paragraph, 3 multiple choice questions have to be answered. Each
question has only one correct answer and carries +4 marks for correct answer and 1 mark for wrong answer.
(v) Section IV contains 3 questions. Each question contains statements given in 2 columns. Statements in the first column
have to be matched with statements in the second column and each question carries +6 marks and marks will be awarded if
all the four parts are correctly matched. No marks will be given for any wrong match in any question. There is no negative
marking.

PART- I (PHYSICS)
SECTION I

Straight Objective Type

This section contains 9 multiple choice questions numbered 1 to 9. Each question has 4 choices (A), (B), (C) and (D), out of
which only one is correct.

1. A circuit is connected as shown in the figure with the switch S open. When the 3F X 6F
switch is closed the total amount of charge that flows from Y to X is
(A) 0 (B) 54C
(C) 27 C (D) 81 C S
3 6
Y

9V
Sol. (C)
27 C

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3F X 6F 3F 6F
+9C X +18C
+18C +18C +9C +36C
S
S
3 6
1A +27C
Y
3 Y 6
9V
9V
Initial charge distribution (when switch S is open) Final charge distribution (when switch S is closed)
2. A long, hollow conducting cylinder is kept coaxially inside another long, hollow conducting cylinder of larger radius.
Both the cylinders are initially electrically neutral.
(A) A potential difference appears between the two cylinders when a charge density is given to the inner cylinder.
(B) A potential difference appears between the two cylinders when a charge density is given to the outer cylinder.
(C) No potential difference appears between the two cylinders when a uniform line charge is kept along the axis of the
cylinders.
(D) No potential difference appears between the two cylinders when same charge density is given to both the
cylinders.
Sol. (A)
dV = E dr

and E =
2 0 r
where r is distance from the axis of cylindrical charge distribution (r is equal to or greater than radius of cylindrical
charge distribution).

3. In the options given below, let E denote the rest mass energy of a nucleus and n a neutron. The correct option is
(A) E ( 236
92 U ) > E ( 137
53 I ) + E ( 39 Y ) + 2E(n)
97
(B) E ( 236
92 U ) < E ( 137
53 I ) + E ( 39 Y ) + 2E(n)
97

(C) E ( 236
92 U ) < E ( 140
56 Ba ) + E ( 36 Kr ) + 2E(n)
94
(D) E ( 236
92 U ) = E ( 140
56 Ba ) + E ( 36 Kr ) + 2E(n)
94

3. (A)
Rest mass energy of U will be greater than the rest mass energy of the nucleus in which it breaks (as conservation of
momentum is always followed)

4. In an experiment to determine the focal length (f) of a concave mirror by the uv method, a student places the object
pin A on the principal axis at a distance x from the pole P. The student looks at the pin and its inverted image from a
distance keeping his/her eye in line with PA. When the student shifts his/her eye towards left, the image appears to the
right of the object pin. Then,
(A) x < f (B) f < x < 2f
(C) x = 2f (D) x > 2f
Sol. (B)
Due to parallax

5. The largest wavelength in the ultraviolet region of the hydrogen spectrum is 122 nm. The smallest wavelength in the
infrared region of the hydrogen spectrum (to the nearest integer) is
(A) 802 nm (B) 823 nm
(C) 1882 nm (D) 1648 nm
Sol. (B)
Transition from to n = 3 will produce smallest wavelength in infrared region.

6. A resistance of 2 is connected across one gap of a metre-bridge (the length of the wire is 100 cm) and an unknown
resistance, greater than 2, is connected across the other gap. When these resistance are interchanged, the balance point
shifts by 20 cm. Neglecting any corrections, the unknown resistance is
(A) 3 (B) 4
(C) 5 (D) 6

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Sol. (A) 2 x
2
= (i) G
x 100
x + 20
= (ii) 100
2 80
Solving (i) and (ii) x = 3

7. A ray of light travelling in water is incident on its surface open to air. The angle of incidence is , which is less than the
critical angle. Then there will be
(A) only a reflected ray and no refracted ray
(B) only a refracted ray and no reflected ray
(C) a reflected ray and a refracted ray and the angle between them would be less than 180 2
(D) a reflected ray and a refracted ray and the angle between them would be greater than 180 2
Sol. (C)
Refracted ray
air
water

Reflected ray
Incident ray

8. Two particle of mass m each are tied at the ends of a light string of length 2a. The F
whole system is kept on a frictionless horizontal surface with the string held tight so
that each mass is at a distance a from the center P (as shown in the figure). Now, the
mid-point of the string is pulled vertically upwards with a small but constant force F. As
m m
a result, the particles move towards each other on the surface. The magnitude of P
acceleration, when the separation between them becomes 2x is a a
F a F x
(A) (B)
2m a x 2
2 2m a x 2
2

F x F a2 x2
(C) (D)
2m a 2m x

Sol. (B)
2T sin = F F
T cos = mA
F a T
2 tan = N T
mA m
P
F x x
A= 2
2m a x 2

mg

9. Consider a neutral conducting sphere. A positive point charge is placed outside the sphere. The net charge on the
sphere is then,
(A) negative and distributed uniformly over the surface of the sphere
(B) negative and appears only at the point on the sphere closest to the point charge
(C) negative and distributed non-uniformly over the entire surface of the sphere
(D) zero

Sol. (D)

SECTION II

Assertion - Reason Type

This section contains 4 questions numbered 10 to 13. Each question contains STATEMENT-1 (Assertion) and STATEMENT-2
(Reason). Each question has 4 choices (A), (B), (C) and (D) out of which ONLY ONE is correct.

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10. STATEMENT-1
The formula connecting u, v and f for a spherical mirror is valid only for mirrors whose sizes are very small compared
to their radii of curvature.
because
STATEMENT-2
Laws of reflection are strictly valid for plane surfaces, but not for large spherical surfaces.
(A) Statement-1 is True, Statement-2 is True; Statement -2 is a correct explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement -2 is NOT a correct explanation for Statement-1.
(C) Statement -1 is True, Statement-2 is False.
(D) Statement -1 is False, Statement-2 is True.
Sol. (C)

11. STATEMENT-1
If the accelerating potential in an X-ray tube is increased, the wavelengths of the characteristic X-rays do not change.
because
STATEMENT -2
When an electron beam strikes the target in an X-ray tube, part of the kinetic energy is converted into X-ray energy.
(A) Statement-1 is True, Statement-2 is True; Statement -2 is a correct explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement -2 is NOT a correct explanation for Statement-1.
(C) Statement -1 is True, Statement-2 is False.
(D) Statement -1 is False, Statement-2 is True.
Sol. (B)

12. STATEMENT-1
A block of mass m starts moving on a rough horizontal surface with a velocity v. It stops due to friction between the
block and the surface after moving through a certain distance. The surface is now tilted to an angle of 300 with the
horizontal and the same block is made to go up on the surface with the same initial velocity v. The decrease in the
mechanical energy in the second situation is smaller than that in the first situation.
because
STATEMENT-2
The coefficient of friction between the block and the surface decreases with the increase in the angle of inclination.
(A) Statement -1 is True, Statement-2 is True; Statement-2 is a correct explanation for statement-1.
(B) Statement -1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for statement-1.
(C) Statement -1 is True, Statement-2 is False.
(D) Statement -1 is False, Statement-2 is True.
Sol. (C)

13. STATEMENT-1
In an elastic collision between two bodies, the relative speed of the bodies after collision is equal to the relative speed
before the collision.
because
STATEMENT-2
In an elastic collision, the linear momentum of the system is conserved.
(A) Statement -1 is True, Statement-2 is True; Statement -2 is a correct explanation for Statement-1.
(B) Statement -1 is True, Statement-2 is True; Statement -2 is NOT a correct explanation for Statement-1.
(C) Statement -1 is True, Statement-2 is False.
(D) Statement -1 is False, Statement-2 is True.
Sol. (B)

SECTION III

Linked Comprehension Type

This section contains 2 paragraphs P14-16 and P17-19. Based upon each paragraph, 3 multiple choice questions have to be
answered. Each question has 4 choices (A), (B), (C) and (D), out of which ONLY ONE is correct.

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P14 16 : Paragraph for Question Nos. 14 to 16

A fixed thermally conducting cylinder has a radius R and height L0. The cylinder is open 2R
at its bottom and has a small hole at its top. A piston of mass M is held at a distance L
from the top surface, as shown in the figure. The atmospheric pressure is P0. L

14. The piston is now pulled out slowly and held at a distance 2L from the top. L0
The pressure in the cylinder between its top and the piston will then be
P
(A) P0 (B) 0
2
P0 Mg P0 Mg
(C) + (D) Piston
2 R 2 2 R 2
Sol. (A)
15. While the piston is at a distance 2L from the top, the hole at the top is sealed. The piston is then released, to a position
where it can stay in equilibrium. In this condition, the distance of the piston from the top is
2P R 2 P R 2 Mg
(A) 2 0 ( 2L ) (B) 0 2 ( 2L )
R P0 + Mg R P0
P R 2 + Mg P R 2
(C) 0 2 ( 2L ) (D) 2 0 ( 2L )
R P0 R P0 Mg

Sol. (D)
Mg + P(R2) = P0R2
P0(2LR2) = P(xR2) (P1`V1 = P2V2 for isothermal process)
P R 2
x = 20 ( 2L )
R P0 Mg

16. The piston is taken completely out of the cylinder. The hole at the top is sealed. A
water tank is brought below the cylinder and put in a position so that the water surface
in the tank is at the same level as the top of the cylinder as shown in the figure. The
density of the water is . In equilibrium, the height H of the water column in the L0
cylinder satisfies
(A) g(L0H)2 + P0(L0 H) + L0P0 = 0 H
(B) g(L0H)2 P0(L0 H) L0P0 = 0
(C) g(L0H)2 + P0(L0 H) L0P0 = 0
(D) g(L0H)2 P0(L0 H) + L0P0 = 0

Sol. (C)
R2P0L0 = P(L0 H)R2 . . . (i)
P = P0 + g(L0 H) . . . (ii)
Solving (i) & (ii), we get the answer.

P17 19 : Paragraph for Question Nos. 17 to 19

Two discs A and B are mounted coaxially on a vertical axle. The discs have moments of inertia I and 2I respectively about the
common axis. Disc A is imparted an initial angular velocity 2 using the entire potential energy of a spring compressed by a
distance x1. Disc B is imparted an angular velocity by a spring having the same spring constant and compressed by a distance
x2. Both the discs rotate in the clockwise direction.

17. The ratio of x1/x2 is

1
(A) 2 (B)
2
1
(C) 2 (D)
2
Sol. (C)
1 2 1
kx1 = I ( 2)
2

2 2

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1 2 1
kx 2 = ( 2I )( )
2

2 2
x1
= 2
x2

18. When disc B is brought in contact with disc A, they acquire a common angular velocity in time t. The average frictional
torque on one disc by the other during this period is
2I 9I
(A) (B)
3t 2t
9I 3I
(C) (D)
4t 2t

Sol. (A)
Applying conservation of angular momentum
I ( 2) + 2I ( ) 4
= = . . . (i)
3I 3

= + t . . . (ii)
2I
2I
From (1) & (ii), =
3t
19. The loss of kinetic energy during the above process is
I2 I2
(A) (B)
2 3
I2 I2
(C) (D)
4 6
Sol. (B)

SECTION IV
Matrix-Match Type
This section contains 3 questions. Each question contains statements given in two columns which have to be matched. Statements
(A, B, C, D) in column I have to be matched with statements (p, q, r, s) in column II. The answers to these questions have to be
appropriately bubbled as illustrated in the following example.
If the correct match are A-p, A-s, B-r, C-p, C-q and D-s, then the correctly bubbled 4 4 matrix should be as follows:
p q r s

A p q r s

B p q r s

C p q r s

D p q r s

20. Some physical quantities are given in Column I and some possible SI units in which these quantities may be expressed
are given in Column II. Match the physical quantities in Column I with the units in Column II and indicate your
answer by darkening appropriate bubbles in the 4 4 matrix given in the ORS.
Column I Column II
(A) GM e M s (p) (volt) (coulomb) (metre)

G universal gravitational constant, M e mass of the earth,

M s mass of the Sun

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3RT (q) (kilogram) (metre)3 (second)2

(B) ; R universal gas constant, T absolute temperature,
M
M molar mass

F 2 (r) (meter)2 (second)2

(C) 2 2 ; F force, q charge, B magnetic field
q B
GM e (s) (farad) (volt)2 (kg)1
(D) , G universal gravitational constant,
Re
M e mass of the earth, R e radius of the earth
Sol. A (p) & (q), B (r) & (s), C (r) & (s), D (r) & (s)
21. Some laws/processes are given in Column I. Match these with the physical phenomena given in Column II and
indicate your answer by darkening appropriate bubbles in the 4 4 matrix given in the ORS.
Column I Column II
(A) Transition between two atomic energy levels (p) Characteristic X-rays
(B) Electron emission from a material (q) Photoelectric effect
(C) Mosleys law (r) Hydrogen spectrum
(D) Change of photon energy into kinetic energy of electrons (s) -decay

Sol. A (p) & (r), B (q) & (s), C (p), D (q)

22. (C)olumn I gives certain situations in which a straight metallic wire of resistance R is used and Column II gives some
resulting effects. Match the statements in Column I with the statements in Column II and indicate your answer by
darkening appropriate bubbles in the 4 4 matrix given in the ORS.
Column I Column II
(A) A charged capacitor is connected to the ends of the wire (p) A constant current flows through the wire

(B) The wire is moved perpendicular to its length with a constant
velocity in a uniform magnetic field perpendicular to the
plane of motion
(C) The wire is placed in a constant electric field that has a
direction along the length of the wire.
(D) A battery of constant emf is connected to the ends of the wire
(q) Thermal energy is generated in the wire
(r) A constant potential difference develops
between the ends of the wire
(s) Charges of constant magnitude appear at
the ends of the wire

Sol. A (q), B (r) & (s), C (r) & (s), D (p), (q) & (r)

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PART- II (CHEMISTRY)
SECTION I

Straight Objective Type

This section contains 9 multiple choice questions numbered 23 to 31. Each question has 4 choices (A), (B), (C) and (D), out of
which ONLY ONE is correct.

23. The number of structural isomers for C6H14 is

(A) 3 (B) 4
(C) 5 (D) 6

Sol. (C)
C6H14
H3C CH2 CH2 CH2 CH2 CH3 H3C CH CH2 CH2 CH3

CH3
H3C CH CH CH2 CH3 H3C CH CH CH3 CH3

CH3 CH3 CH3 H3C C CH2 CH3

CH3
Hence (C) is correct.

24. In the following reaction,

O
conc. HNO

conc. H SO
3
X
N 2 4

the structure of the major product X is

(A) (B) O2 N
O O
NO2
N N
H H

(C) (D)
O O

N O2 N N
H H

NO2
Sol. (B)

O O

conc. HNO
N C 3
conc. H 2SO 4
O2 N NH C

H
Due to presence of lone pair of electron on nitrogen atom, it will activate the ring and it will stabilize
intermediate cation at o and p positions.
Hence (B) is correct.

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25. When 20 g of naphthoic acid (C11H8O2) is dissolved in 50 g of benzene (Kf = 1.72 K kg mol1), a freezing point
depression of 2 K is observed. The vant Hoff factor (i) is
(A) 0.5 (B) 1
(C) 2 (D) 3
Sol. (A)
Tf = Kf molality i
20 1000
2 = 1.72 i
172 50
i = 0.5
Hence (A) is correct.
26. Among the following, the paramagnetic compound is
(A) Na2O2 (B) O3
(C) N2O (D) KO2
Sol. (D)
O 22 = 1s 2 *1s 2 , 2s 2 * 2s 2 , 2p z2 , 2p 2x = 2p 2y , * 2p 2x = * 2p 2y
Number of unpaired electrons = 0.
N = N O Number of unpaired electrons = 0

O O O O O O Number of unpaired electrons = 0

O 2 2 2 2
= 1s , *1s 2s , * 2s , 2
2p 2z , 2p2x = 2p 2y , * 2p2x
= * 2p1y
Number of unpaired electrons = 1
Thus O 2 is paramagnetic.
Hence (D) is correct.

27. The value of log10K for a reaction A B is

(Given : r H 298K = 54.07kJ mol , rS298K = 10JK 1mol 1and R= 8.314 JK1mol1; 2.3038.314298 = 5705)
1

(A) 5 (B) 10
(C) 95 (D) 100
Sol. (B)
G = H TS = 54.07 1000 298 10 = 57050 J mol1
57050 = 5705 log10K
log10K = 10
Hence (B) is correct

28. The species having bond order different from that in CO is

(A) NO (B) NO+

(C) CN (D) N2
Sol. (A)
NO (16 electron system)
Bond order = 2.
NO, CN and N2 are isoelectronic with CO therefore all have same bond order (= 3)
Hence (A) is correct.
29. The percentage of p-character in the orbitals forming PP bonds in P4 is
(A) 25 (B) 33
(C) 50 (D) 75
Sol. (D)
P is sp3 hybridized in P4.
P

P P

P
Hence (D) is correct.

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30. Extraction of zinc from zinc blende is achieved by

(A) electrolytic reduction (B) roasting followed by reduction with carbon
(C) roasting followed by reduction with another metal (D) roasting followed by self-reduction

Sol. (B)
Option (B) is correct.

31. The reagent(s) for the following conversion,

Br ?
Br H H
is/are
(A) alcoholic KOH (B) alcoholic KOH followed by NaNH2
(C) aqueous KOH followed by NaNH2 (D) Zn/CH3OH
Sol. (B)

H2 C CH2
Alc. KOH
H2 C NaNH
CH HC
2
CH
Br Br
Br
Because CH2 = CH Br has partial C Br double bond character, it requires more stronger base to remove
HBr.
Hence(B) is correct.

SECTION II

Assertion-Reason Type

This section contains 4 questions numbered 32 to 35. Each question contains STATEMENT-1 (Assertion) and STATEMENT-2
(Reason). Each question has 4 choices (A), (B), (C) and (D) out of which ONLY ONE is correct.

32. STATEMENT-1: p-Hydroxybenzoic acid has a lower boiling point than o-hydroxybenzoic acid.
because
STATEMENT-2: o-Hydroxybenzoic acid has intramolecular hydrogen bonding.
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1.
(C) Statement-1 is True, Statement -2 is False.
(D) Statement-1 is False, Statement-2 is True.

Sol. (D)
O H
O
C OH
More stabilized by intramolecular hydrogen bonding

H O
H
O O C
More stronger intermolecular forces increases the boiling point.

C O O
H
O H
Hence (D) is correct.

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33. STATEMENT-1: Micelles are formed by surfactant molecules above the critical micellar concentration (CMC).
because
STATEMENT-2: The conductivity of a solution having surfactant molecules decreases sharply at the CMC.
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1.
(C) Statement-1 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.
Sol. (B)
The formation of micelles takes places only above a particular temperature called Kraft temperature (Tk) and above a
particular concentration called critical micelle concentration (CMC).
Each micelle contains at least 100 molecules. Therefore conductivity of the solution decreases sharply at the CMC.
Hence (B) is correct.

34. STATEMENT-1: Boron always forms covalent bond.

because
STATEMENT-2: The small size of B3+ favours formation of covalent bond.
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1.
(C) Statement-1 is True, Statement-2 is True.
(D) Statement-1 is False, Statement-2 is True.
Sol. (A)
According to Fajans rule small cations having high charge density always have tendency to form covalent bond.
Hence (A) is correct

35. STATEMENT-1: In water, orthoboric acid behaves as a weak monobasic acid.

because
STATEMENT-2: In water, orthoboric acid acts as a proton donor.
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1.
(C) Statement-1is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.

Sol. (C)
H3BO3 (orthoboric acid) is a weak lewis acid.

H 3BO3 + H 2O B ( OH )4 + H
It does not donate proton rather it acceptors OH form water.
Hence (C) is correct

SECTION III

Linked Comprehension Type

This section contains 2 paragraphs C36-38 and C39-41. Based upon each paragraph, 3 multiple choice questions have to be
answered. Each question has 4 choices (A), (B), (C) and (D), out of which ONLY ONE is correct.

C36-38 : Paragraph for question Nos 36 to 38

Chemical reactions involve interaction of atoms and molecules. A large number of atoms/molecules (approximately 6.023 1023)
are present in a few grams of any chemical compound varying with their atomic/molecular masses. To handle such large numbers
conveniently, the mole concept was introduced. This concept has implications in diverse areas such as analytical chemistry,
biochemistry, electrochemistry and radiochemistry. The following example illustrates a typical case, involving
chemical/electrochemical reaction, which requires a clear understanding of the mole concept.

A 4.0 molar aqueous solution of NaCl is prepared and 500 mL of this solution is electrolysed. This leads to the evolution of
chlorine gas at one of the electrodes (atomic mass: Na = 23, Hg = 200; 1 Faraday=96500 coulombs)

36. The total number of moles of chlorine gas evolved is

(A) 0.5 (B) 1.0
(C) 2.0 (D) 3.0

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Sol. (B)
Na + + Cl
NaCl
At anode:
2Cl Cl2
Moles of Cl = 2 in 500 ml.
Therefore 1 mole of Cl2 evolves.
Hence (B) is correct.

37. If the cathode is a Hg electrode, the maximum weight (g) of amalgam formed from this solution is
(A) 200 (B) 225
(C) 400 (D) 446
Sol. (D)
Na Hg (amalgam) formed = 2 moles at cathode.
Hence (D) is correct.

38. The total charge (coulombs) required for complete electrolysis is

(A) 24125 (B) 48250
(C) 96500 (D) 193000
Sol. (D)
2 moles of electrons (2 Faraday) are required.
1F = 96500
2F = 193000
Hence (D) is correct.

C39-41: Paragraph for Question Nos. 39 to 41

The noble gases have closed-shell electronic configuration and are monoatomic gases under normal conditions. The low boiling
points of the lighter noble gases are due to weak dispersion forces between the atoms and the absence of other interatomic
interactions.
The direct reaction of xenon with fluorine leads to a series of compounds with oxidation numbers +2, +4 and +6. XeF 4 reacts
violently with water to give XeO3. The compounds of xenon exhibit rich stereochemistry and their geometries can be deduced
considering the total number of electron pairs in the valence shell.

39. Argon is used in arc welding because of its

(A) low reactivity with metal (B) ability to lower the melting point of metal
(C) flammability (D) high calorific value
Sol. (A)
Argon is used mainly to provide an inert atmosphere in high temperature metallurgical (arc welding of metals/alloys)
extraction.
Hence (A) is correct.

40. The structure of XeO3 is

(A) linear (B) planar
(C) pyramidal (D) T-shaped
Sol. (C)
Xe
O O
sp3 hybridized pyramidal structure.
O
Hence (C) is correct.

41. XeF4 and XeF6 are expected to be

(A) oxidizing (B) reducing
(C) unreactive (D) strongly basic
Sol. (A)
6XeF4 + 12H 2O
4Xe + 2XeO3 + 24HF + 3O 2
XeF6 + 3H 2O
XeO3 + 6HF
Hence (A) is correct.

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SECTION IV

Matrix-Match Type

This section contains 3 questions. Each question contains statements given in two columns which have to be matched. Statements
(A, B, C, D) in Column-I have to be matched with statements (p, q, r, s) in Column-II. The answers to these questions have to be
appropriately bubbled as illustrated in the following example.

If the correct matches are A-p, A-s, B-q, B-r, C-p, C-q and D-s, then the correctly bubbled 4 4 matrix should be as follows:
p q r s
A p q r s
B p q r s
C p q r s
D p q r s

42. Match the complexes in Column-I with their properties listed in Column-II. Indicate your answer by darkening the
appropriate bubbles of the 4 4 matrix given in the ORS.
Column-I Column-II
(A) [Co(NH3)4(H2O)2]Cl2 (p) geometrical isomers
(B) [Pt(NH3)2Cl2] (q) paramagnetic
(C) [Co(H2O)5Cl]Cl (r) diamagnetic
(D) [Ni(H2O)6]Cl2 (s) metal ion with +2 oxidation state
Sol. A p, q, s B p, r, s C q, s D q, s
(A)
2+ 2+
OH2 NH3
NH3 OH2
H3N H2O
Co Co
H3N NH3 H 3N NH3
OH2 OH2

(trans) (cis)
Co2+ = 3d7 (Paramagnetic)
(B) [Pt(NH3)2Cl2] is square planar.
Cl Cl
H3N H3N
2+ 2+
Pt Pt
H3N Cl Cl NH3

(cis) (trans)
Pt2+ = 5d84s0 (diamagnetic)
(C) (D)
+ 2+
OH2
OH2
OH2
H2O OH2
H 2O
Co
H 2O OH2 Co

Cl H2O OH2
OH2
Co2+ = 3d7 (paramagnetic) Ni2+ = 3d8 (weak field ligand, paramagnetic)

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43. Match gases under specified conditions listed in Column-I with their properties/laws in Column-II. Indicate your
answer by darkening the appropriate bubsbles of the 4 4 matrix given in the ORS.
Column-I Column-II
(A) hydrogen gas (P = 200 atm, T = 273K) (p) compressibility factor 1
(B) hydrogen gas (P 0, T = 273K) (q) attractive forces are dominant
(C) CO2 (P = 1 atm, T = 273K) (r) PV = nRT
(D) real gas with very large molar volume (s) P(V nb) = nRT

Sol. A p, s B r C p, q D p, s
PVm
(A) Z = at high pressure and low temperature.
RT
an 2
Equation P + 2 ( V nb ) = nRT reduces to P(V nb) = nRT.
V
(B) For hydrogen gas value of Z = 1 at P = 0 and it increase continuously on increasing pressure.
(C) CO2 molecules have larger attractive forces, under normal conditions.
PV
(D) Z = m , at very large molar volume Z 1.
RT

44. Match the chemical substances in Column-I with type of polymers/type of bonds in Column-II. Indicate your answer by
darkening the appropriate bubbles of the 4 4 matrix given in the ORS.
Column-I Column-II
(A) cellulose (p) natural polymer
(B) nylon-6, 6 (q) synthetic polymer
(C) protein (r) amide linkage
(D) sucrose (s) glycoside linkage

Sol. A p, s, B q, r; C p, r Ds
(A) Cellulose
O O O
O O

(Glycoside linkage)
(B) Nylon 6, 6
H O

N C
C N

O
(Amide linakge)
(C) Protein
H O
R H
C N C
N C N
R' H
H O H
(Amide linkage)
(D) Sucrose
CH2OH
H O H
H
OH H O CH2OH
OH O OH H
H OH H
H OH
(Glycoside linkage)

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PART III (MATHEMATICS)

SECTION I

Straight Objective Type

This section contains 9 multiple choice questions numbered 45 to 53. Each question has 4 choices (A), (B), (C) and (D), out of
which ONLY ONE is correct.

45. A hyperbola, having the transverse axis of length 2 sin, is confocal with the ellipse 3x2 + 4y2 = 12. Then its equation is
(A) x2 cosec2 y2 sec2 = 1 (B) x2 sec2 y2 cosec2 = 1
2 2 2 2
(C) x sin y cos = 1 (D) x2 cos2 y2 sin2 = 1

Sol. (A)
x 2 y2
The given ellipse is + =1
4 3
1
a = 2, b = 3 3 = 4 (1 e2) e =
2
so that ae = 1
Hence the eccentricity e1, of the hyperbola is given by
1 = e1sin e1 = cosec
b2 = sin2(cosec2 1) = cos2
x2 y2
Hence the hyperbola is = 1 or x2cosec2 y2sec2 = 1
sin cos 2
2

46. The tangent to the curve y = ex drawn at the point (c, ec) intersects the line joining the points (c 1, ec1) and
(c + 1, ec+1)
(A) on the left of x = c (B) on the right of x = c
(C) at no point (D) at all points

Sol. (A) B
y
Slope of the line joining the points (c 1, ec 1) and (c + 1, ec + 1) is equal
ec +1 ec 1
to > ec
2
tangent to the curve y = ex will intersect the given line to the left of the A
line x = c. (c, ec)
Alternative x
The equation of the tangent to the curve y = ex at (c, ec) is O
y ec = ec(x c) (1)
Equation of the line joining the given points is
ec (e e1 )
y ec 1 = [x (c 1)] (2)
2
Eliminating y from (1) and (2), we get
[x (c 1)] [2 (e e1)] = 2e1
e + e1 2
or x c = < 0 x < c.
2 (e e1 )
the line (1) and (2) meet on the left of the line x = c.

47. A man walks a distance of 3 units from the origin towards the north-east (N 45 E) direction. From there, he walks a
distance of 4 units towards the north-west (N 45 W) direction to reach a point P. Then the position of P in the Argand
plane is
(A) 3ei/4 + 4i (B) (3 4i) ei/4
i/4
(C) (4 + 3i) e (D) (3 + 4i) ei/4

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Sol. (D) P y
Let OA = 3, so that the complex number 4
associated with A is 3ei/4. 3ei/4
If z is the complex number associated with P, A
3
z 3ei / 4 4 i / 2 4i /4
then = e = x
0 3ei / 4 3 3 O
3z 9ei/4 = 12iei/4
z = (3 + 4i)ei/4.

48. Let f(x) be differentiable on the interval (0, ) such that f(1) = 1, and
t 2f ( x ) x 2f ( t )
lim =1
t x tx
for each x > 0. Then f(x) is
1 2x 2 1 4x 2
(A) + (B) +
3x 3 3x 3
1 2 1
(C) + 2 (D)
x x x

Sol. (A)

t 2f (x) x 2f (t)
lim =1
t x tx
x2f(x) 2xf(x) + 1 = 0
1
f(x) = cx2 + also f(1) = 1
3x
2
c= .
3
2 1
Hence f(x) = x 2 + .
3 3x

49. The number of solutions of the pair of equations

2 sin2 cos2 = 0
2 cos2 3 sin = 0
in the interval [0, 2] is
(A) zero (B) one
(C) two (D) four

Sol. (C)
1
2sin2 cos2 = 0 sin2 =
4
1
also 2cos2 = 3sin sin =
2
two solutions in [0, 2].

50. Let , be the roots of the equation x2 px + r = 0 and , 2 be the roots of the equation x2 qx + r = 0. Then the
2
value of r is
2 2
(A) ( p q )( 2q p ) (B) ( q p )( 2p q )
9 9
2 2
(C) ( q 2p )( 2q p ) (D) ( 2p q )( 2q p )
9 9

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Sol. (D)
The equation x2 px + r = 0 has roots (, ) and the equation

x2 qx + r = 0 has roots , 2 .
2

r = and + = p and + 2 = q
2
2q p 2(2p q)
= and =
3 3
2
= r = (2q p) (2p q).
9

51. The number of distinct real values of , for which the vectors 2 i + j + k , i 2 j + k and i + j 2 k are
coplanar, is
(A) zero (B) one
(C) two (D) three

Sol. (C)
2 1 1
6 2
1 2 1 = 0 3 2 = 0
1 1 2
(1 + 2)2 (2 2) = 0 = 2.

52. One Indian and four American men and their wives are to be seated randomly around a circular table. Then the
conditional probability that the Indian man is seated adjacent to his wife given that each American man is seated
adjacent to his wife is
(A) 1/2 (B) 1/3
(C) 2/5 (D) 1/5

Sol. (C)
Let E = event when each American man is seated adjacent to his wife
A = event when Indian man is seated adjacent to his wife
Now, n(A E) = (4!) (2!)5
Even when each American man is seated adjacent to his wife
Again n(E) = (5!) (2!)4
5
A n(A E) (4!) (2!) 2
P = = 4
= .
E n(E) (5!) (2!) 5
Alternative
Fixing four American couples and one Indian man in between any two couples; we have 5 different ways in which his
wife can be seated, of which 2 cases are favorable.
2
required probability = .
5

sec2 x

f ( t ) dt
2
53. lim equals
x
2
4 x2
16
8 ( ) 2 ( )
(A) f 2 (B) f 2

2 1
(C) f (D) 4f(2)
2

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Sol. (A)
sec 2 x

f (t)dt
0
2
lim 2 form
x
0
4 x2
16
f (sec 2 x)2sec x sec x tan x
Let L = lim
x
2x
4
2f (2) 8f (2)
L= = .
/4

SECTION II

Assertion Reason Type

This section contains 4 questions numbered 54 to 57. Each question contains STATEMENT 1 (Assertion) and STATEMENT -2
(Reason). Each question has 4 choices (A), (B), (C) and (D) out of which ONLY ONE is correct.

54. Let the vectors PQ, QR, RS, ST, TU and UP represent the sides of a regular hexagon.

STATEMENT -1 : PQ ( RS + ST ) 0 .

because

STATEMENT -2 : PQ RS = 0 and PQST 0 .

(A) Statement -1 is True, Statement -2 is True; Statement-2 is a correct explanation for Statement-1
(B) Statement -1 is True, Statement -2 is True; Statement-2 is NOT a correct explanation for Statement-1
(C) Statement -1 is True, Statement -2 is False
(D) Statement -1 is False, Statement -2 is True
Sol. (C) T S

Since PQ / TR TR is resultant of SR and ST vector.

(
PQ RS + ST 0 . ) U R

But for statement 2, we have PQ RS = 0

which is not possible as PQ / RS .
P Q
Hence, statement 1 is true and statement 2 is false.

55. Let F(x) be an indefinite integral of sin2x.

STATEMENT -1 : The function F(x) satisfies F(x + ) = F(x) for all real x.
because
STATEMENT -2 : sin2(x + ) = sin2x for all real x.
(A) Statement -1 is True, Statement -2 is True; Statement-2 is a correct explanation for Statement-1
(B) Statement -1 is True, Statement -2 is True; Statement-2 is NOT a correct explanation for Statement-1
(C) Statement -1 is True, Statement -2 is False
(D) Statement -1 is False, Statement -2 is True
Sol. (D)
1 cos 2x
sin xdx =
2
F(x) = dx
2
1
F(x) = (2x sin2x) + c.
4
Since, F(x + ) F(x).
Hence statement 1 is false.
But statement 2 is true as sin2x is periodic with period .

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56. Let H1, H2, , Hn be mutually exclusive and exhaustive events with P(Hi) > 0, i = 1, 2, , n. Let E be any other event
with 0 < P(E) < 1.
STATEMENT -1 : P(Hi | E) > P(E | Hi) . P(Hi) for i = 1, 2, , n
because
n
STATEMENT -2 : P ( Hi ) = 1
i =1
(A) Statement -1 is True, Statement -2 is true; Statement-2 is a correct explanation for Statement-1
(B) Statement -1 is True, Statement -2 is True; Statement-2 is NOT a correct explanation for Statement-1
(C) Statement -1 is True, Statement -2 is False
(D) Statement -1 is False, Statement -2 is True
Sol. (D)
Statement : 1
H E
If P(Hi E) = 0 for some i, then P i = P = 0
E Hi
If P(Hi E) 0 for i = 1, 2 n, then
H P(H i E) P(H i )
P i =
E P(H i ) P(E)
E
P P(H i )
H E
= i > P P(H i ) [as 0 < P(E) < 1]
P(E) Hi
Hence statement 1 may not always be true.
Statement : 2
Clearly H1 H2 Hn = S (sample space)
P(H1) + P(H2) + + P(Hn) = 1.

57. Tangents are drawn from the point (17, 7) to the circle x2 + y2 = 169.

STATEMENT -1 : The tangents are mutually perpendicular.

because
STATEMENT -2 : The locus of the points from which mutually perpendicular tangents can be drawn to the given
circle is x2 + y2 = 338
(A) Statement -1 is True, Statement -2 is true; Statement-2 is a correct explanation for Statement-1
(B) Statement -1 is True, Statement -2 is true; Statement-2 is NOT a correct explanation for Statement-1
(C) Statement -1 is True, Statement -2 is False
(D) Statement -1 is False, Statement -2 is True
Sol. (A)
Since the tangents are perpendicular locus of perpendicular tangents to circle
x2 + y2 = 169 is a director circle having equation x2 + y2 = 338.

SECTION III

Linked Comprehension Type

This section contains 2 paragraphs M5860 and M6163. Based upon each paragraph, 3 multiple choice questions have to be
answered. Each question has 4 choice (A), (B), (C) and (D), out of which ONLY ONE is correct.
M5860 : Paragraph for question Nos. 58 to 60
Consider the circle x + y = 9 and the parabola y2 = 8x. They intersect at P and Q in the first and the fourth quadrants,
2 2

respectively. Tangents to the circle at P and Q intersect the x-axis at R and tangents to the parabola at P and Q intersect the x-axis
at S.
58. The ratio of the areas of the triangles PQS and PQR is
(A) 1 : 2 (B) 1 : 2
(C) 1 : 4 (D) 1 : 8

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Sol. (C) Y

( ) (
Coordinates of P and Q are 1, + 2 2 and 1, 2 2 . )
P
1
Area of PQR = 4 2 8 = 16 2 (1, 2 2)
2
R
1 S (1, 0)
Area of PQS = 4 2 2 = 4 2 O X
2 (3, 0) (1, 0)
(9, 0)
Ratio of area of triangle PQS and PQR is 1 : 4.
Q
(1, 2 2)

59. The radius of the circumcircle of the triangle PRS is

(A) 5 (B) 3 3
(C) 3 2 (D) 2 3
Sol. (B)
Equation of circumcircle of PRS is (x + 1) (x 9) + y2 + y = 0
( )
It will pass through 1, 2 2 , then 16 + 8 + . 2 2 = 0
8
= =2 2
2 2
Equation of circumcircle is x2 + y2 8x + 2 2y 9 = 0 .
Hence its radius is 3 3 .
Alternative
Let PSR =
2 2
sin =
2 3
PR = 6 2 = 2R sin R = 3 3 .

60. The radius of the incircle of the triangle PQR is

(A) 4 (B) 3
(C) 8/3 (D) 2
Sol. (D)

Radius of incircle is r =
s
as = 16 2
6 2 +6 2 +4 2
s= =8 2
2
16 2
r= =2.
8 2

M6163 : Paragraph for Question Nos. 61 to 63

Let Vr denote the sum of the first r terms of an arithmetic progression (A.P.) whose first term is r and the common difference is
(2r 1). Let
Tr = Vr+1 Vr 2 and Qr = Tr+1 Tr for r = 1, 2,

61. The sum V1 + V2 + + Vn is

1 ( 1 (
(A) n n + 1) ( 3n 2 n + 1) (B) n n + 1) ( 3n 2 + n + 2 )
12 12
1 1
(C) n ( 2n 2 n + 1) (D) ( 2n 3 2n + 3)
2 3

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 IIT-JEE2007-PAPER-I-21

Sol. (B)
r 1
Vr = [2r + (r 1)(2r 1)] = (2r3 r2 + r)
2 2
1
Vr = 12 n(n + 1)(3n + n + 2).
2

62. Tr is always
(A) an odd number (B) an even number
(C) a prime number (D) a composite number
Sol. (D)
1 1
Vr + 1 Vr = (r + 1)3 r3 [(r + 1)2 r2] + (1)
2 2
= 3r2 + 2r + 1
Tr = 3r2 + 2r 1 = (r + 1)(3r 1)
which is a composite number.

63. Which one of the following is a correct statement?

(A) Q1, Q2, Q3, are in A.P. with common difference 5
(B) Q1, Q2, Q3, are in A.P. with common difference 6
(C) Q1, Q2, Q3, are in A.P. with common difference 11
(D) Q1 = Q2 = Q3 =
Sol. (B)
Tr = 3r2 + 2r 1
Tr + 1 = 3(r + 1)2 + 2(r + 1) 1
Qr = Tr + 1 Tr = 3[2r + 1] + 2[1]
Qr = 6r + 5
Qr + 1 = 6(r + 1) + 5
Common difference = Qr + 1 Qr = 6.
SECTION IV
Matrix-Match Type
This section contains 3 questions. Each question contains statements given in two columns which have to be matched. Statements
(A, B, C, D) in Column I have to be matched with statements (p, q, r, s) in Column II. The answers to these questions have to be
appropriately bubbled as illustrated in the following example.
If the correct matches are Ap, As, Bq, Br, Cp, Cq and Ds, then the correctly bubbled 4 4 matrix should be as follows:
p q r s
A p q r s
B p q r s
C p q r s
D p q r s

64. Consider the following linear equations

ax + by + cz = 0
bx + cy + az = 0
cx + ay + bz = 0
Match the conditions / expressions in Column I with statements in Column II and indicate your answers by darkening
the appropriate bubbles in 4 4 matrix given in the ORS.
Column I Column II
(A) a + b + c 0 and a2 + b2 + c2 = ab + bc + ca (p) the equations represent planes meeting only at a single
point.
(B) a + b + c = 0 and a2 + b2 + c2 ab + bc + ca (q) the equations represent the line x = y = z.
2 2 2
(C) a + b + c 0 and a + b + c ab + bc + ca (r) the equations represent identical planes.
(D) a + b + c = 0 and a2 + b2 + c2 = ab + bc + ca (s) the equations represent the whole of the three dimensional
space.

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 IIT-JEE2007-PAPER-I-22

Sol. Ar Bq Cp Ds

a b c
1
= b c a = (a + b + c)[(a b)2 + (b c)2 + (c a)2]
c a b 2

(A). If a + b + c 0 and a2 + b2 + c2 = ab + bc + ca
= 0 and a = b = c 0
the equations represent identical planes.

(B). a + b + c = 0 and a2 + b2 + c2 ab + bc + ca
= 0 the equations have infinitely many solutions.
ax + by = (a + b)z
bx + cy = (b + c)z
(b2 ac)y = (b2 ac)z y = z
ax + by + cy = 0 ax = ay x = y = z.

(C). a + b + c 0 and a2 + b2 + c2 ab + bc + ca
0 the equation represent planes meeting at only one point.

(D). a + b + c = 0 and a2 + b2 + c2 = ab + bc + ca a = b = c = 0
the equation represent whole of the three dimensional space.

65. Match the integrals in Column I with the values in Column II and indicate your answer by darkening the appropriate
bubbles in the 4 4 matrix given in the ORS.
Column I Column II
1
dx 1 2
(A) 1 + x2 (p)
2
log
3
1

1
dx 2
(B) 1 x 2
(q) 2log
3
0

3
dx
(r)
(C) 1 x2 3
2

2
dx
(s)
(D) x 2
x 1
2
1

Sol. As Bs Cp Dr

1
dx
(A). 1 + x2 = 2
1

1
dx
(B). 1 x 2
=
2
0

3
dx 1 2
(C). 1 x 2 = 2 ln 3
2

2
dx
(D). x x 1 2
=
3
1

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 IIT-JEE2007-PAPER-I-23

66. In the following [x] denotes the greatest integer less than or equal to x.
Match the functions in Column I with the properties Column II and indicate your answer by darkening the appropriate
bubbles in the 4 4 matrix given in the ORS.
Column I Column II
(A) x |x| (p) continuous in (1, 1)
(B) x (q) differentiable in (1, 1)

(C) x + [x] (r) strictly increasing in (1, 1)

(D) |x 1| + |x + 1| (s) not differentiable at least at one point in (1, 1)

Sol. A p, q, r B p, s C r, s D p, q

(A). x|x| is continuous, differentiable and strictly increasing in ( 1, 1).

(B). x is continuous in ( 1, 1) and not differentiable at x = 0.

(C). x + [x] is strictly increasing in ( 1, 1) and discontinuous at x = 0 not differentiable at x = 0.

(D). |x 1| + |x + 1| = 2 in ( 1, 1)
the function is continuous and differentiable in ( 1, 1).

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 IIT-JEE - 2010

Paper-2

Chemistry
Section-1
Single Correct Choice Type
This section contains 6 multiple choice questions. Each question has 4 choices (A), (B), (C) and (D) out of
which ONLY ONE is correct.
1.
In the reaction T, the structure of the product T is

1)

2)

3)

4)

2. Assuming that Hunds rule is violated, the bond order and magnetic nature of the diatomic molecule
B2 is
1) 1 and diamagnetic
2) 0 and diamagnetic
3) 1 and paramagnetic
4) 0 and paramagnetic

3. The species having pyramidal shape is

1) SO3
2) BrF 3
3) SiO32-

4) OSF 2

4. The complex showing a spin-only magnetic moment of 2.82 B.M. is

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 1) Ni(CO)4
2) [NiCl4]2
3) Ni(PPh3)4
4) [Ni(CN)4]2

5. The compounds P, Q and S

P.

Q.

S.

were separately subjected to nitration using HNO3/H2SO4 mixture. The major product formed in each
case respectively, is
1)

2)

3)

4)

6. The packing efficiency of the two-dimensional square unit cell shown below is

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 1) 39.27%
2) 68.02%
3) 74.05%
4) 78.54%

Section-2
Integer Type
This section contains a group of 5 questions. The answer to each of the questions is a Single-digit Integer,
ranging from 0 to 9. The correct digit below the equation number in the ORS is to be bubbled.
7. Among the following, the number of elements showing only one non-zero oxidation state is
O, Cl, F, N, P, Sn, Tl, Na, Ti
1) 0
2) 1
3) 2
4) 3
5) 4
6) 5
7) 6
8) 7
9) 8
10) 9

8. The total number of diprotic acids among the following is

H3PO4 H2SO4 H3PO3 H2CO3 H2S2O7
H3BO3 H3PO2 H2CrO4 H2SO3

1) 0
2) 1
3) 2
4) 3
5) 4
6) 5
7) 6
8) 7
9) 8
10) 9

9. One mole of an ideal gas is taken from a to b along two paths denoted by the solid and the dashed
lines as shown in the graph below. If the work done along the solid line path is Ws and that along the
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 dotted line path is Wd, then the integer closest to the ratio Wd/Ws is

1) 0
2) 1
3) 2
4) 3
5) 4
6) 5
7) 6
8) 7
9) 8
10) 9

10. Total number of geometrical isomers for the complex [RhCl(CO)(PPh3)(NH3)] is

1) 0
2) 1
3) 2
4) 3
5) 4
6) 5
7) 6
8) 7
9) 8
10) 9

11. Silver (atomic weight = 108 g mol1) has a density of 10.5 g cm 3. The number of silver atoms on a
surface of area 1012 m 2 can be expressed in scientific notation as y 10x. The value of x is
1) 0
2) 1
3) 2
4) 3
5) 4
6) 5
7) 6
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 8) 7
9) 8
10) 9

Section-3
Paragraph Type
This section contains 2 paragraphs. Based upon each of the paragraphs 3 multiple choice questions have
to be answered. Each of these questions has four choices (A), (B), (C) and (D) out of which ONLY ONE is
correct.
Directions for question 12 to 14 :
The hydrogen-like species Li2+ is in a spherically symmetric state S1 with one radial node. Upon
absorbing light the ion undergoes transition to a state S2. The state S2 has one radial node and its
energy is equal to the ground state energy of the hydrogen atom.
12. The state S1 is
1) 1s 2) 2s 3) 2p 4) 3s

13. Energy of the state S1 in units of the hydrogen atom ground state energy is
1) 0.75 2) 1.50 3) 2.25 4) 4.50

14. The orbital angular momentum quantum number of the state S2 is

1) 0 2) 1 3) 2 4) 3

Directions for question 15 to 17 :

Two aliphatic aldehydes P and Q react in the presence of aqueous K2CO3 to give compound R, which
upon treatment with HCN provides compound S. On acidification and heating, S gives the product
shown below :

15. The compounds P and Q respectively are

1)

2)

3)

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 4)

16. The compound R is

1)

2)

3)

4)

17. The compound S is

1)

2)

3)

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 4)

Section-4
Matrix Type
This section contains 2 questions. Each question has four choices (A), (B), (C) and (D) given in Column I
and five statements (p), (q), (r), (s) and (t) in Column II. Any given statement in Column I can have correct
matching with one or more statement(s) given in Column II. For example, if for a given question, statement
B matches with the statements given in (q) and (r), then for that particular question, against statement B,
darken the bubbles corresponding to (q) and (r) in ORS.
18. All the compounds listed in Column I react with water. Match the result of the respective reactions with
the appropriate options listed in Column II.
Column I Column II
A (CH3)2SiCl2 p Hydrogen halide formation
B XeF 4 q Redox reaction
C Cl2 r Reacts with glass
D VCl5 s Polymerization
t O2 formation

1) A-p
2) A-q
3) A-r
4) A-s
5) A-t
6) B-p
7) B-q
8) B-r
9) B-s
10) B-t
11) C-p
12) C-q
13) C-r
14) C-s
15) C-t
16) D-p
17) D-q
18) D-r
19) D-s
20) D-t

19. Match the reactions in Column I with appropriate option in Column II.
Column I Column II

Racemic
A p
mixture

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 Addition
B q
reaction

Substitution
C r
reaction

Coupling
D s
reaction
Carbocation
t
intermediate

1) A-p
2) A-q
3) A-r
4) A-s
5) A-t
6) B-p
7) B-q
8) B-r
9) B-s
10) B-t
11) C-p
12) C-q
13) C-r
14) C-s
15) C-t
16) D-p
17) D-q
18) D-r
19) D-s
20) D-t

Mathematics
Section-1
Single Correct Choice Type
This section contains 5 multiple choice questions. Each question has 4 choices (A), (B), (C) and (D) out of
which ONLY ONE is correct.
20.
Let f be a real-valued function defined on the interval (-1, 1) such that e -x f(x) = 2 + dt, for

all x (1, 1), and let f1 be the inverse function of f. Then (f1) (2) is equal to
1) 1 2) 1/3 3) 1/2 4) 1/e

21. A signal which can be green or red with probability (4/5) and (1/5) respectively, is received by station
A and then transmitted to station B. The probability of each station receiving the signal correctly is
(3/4). If the signal received at station B is green, then the probability that the original signal was green
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 is
1) 3/5 2) 6/7 3) 20/23 4) 9/20

22. Let S = {1, 2, 3, 4}. The total number of unordered pairs of disjoint subsets of S is equal to
1) 25 2) 34 3) 42 4) 41

23. For r = 0, 1,. ., 10, let Ar, Br and Cr denote, respectively, the coefficient of xr in the expansions of (1 +

x)10, (1 + x)20 and (1 + x)30. Then (B10Br - C10Ar) is equal to

1) B10 C10
2) A10(B210 C10A10)
3) 0
4) C10 B10

24. If the distance of the point P(1, 2, 1) from the plane x + 2y 2z =, where > 0, is 5, then the foot
of the perpendicular from P to the plane is
1) (8/3, 4/3, -(7/3))
2) (4/3, -(4/3), 1/3)
3) (1/3, 2/3, 10/3)
4) (2/3, -(1/3), 5/2)

25. Two adjacent sides of a parallelogram ABCD are given by

AB = 2i + 10j + 11k and AD = -i + 2j + 2k.
The side AD is rotated by an acute angle in the plane of the parallelogram so that AD becomes AD.
If AD makes a right angle with the side AB, then the cosine of the angle is given by
1) 8/9
2) (17)/9
3) 1/9
4) 4(5)/9

Section-2
Integer Type
This Section contains 5 questions. The answer to each question is a single-digit integer, ranging from 0 to
9. The correct digit below the question no. in the ORS is to be bubbled.
26. Let f be a function defined on R (the set of all real numbers) such that
f ' (x) = 2010 (x 2009) (x 2010) 2 (x 2011)3 (x 2012)4, for all x R.
If g is a function defined on R with values in the interval (0, ) such that f(x) = ln (g(x)), for all x R,
then the number of points in R at which g has a local maximum is
1) 0
2) 1
3) 2
4) 3
5) 4
6) 5
7) 6
8) 7

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 9) 8
10) 9

27. Two parallel chords of a circle of radius 2 are at a distance (3) + 1 apart. If the chords subtend at the
center, angles of (/k) and (2/k), where k > 0, then the value of [k] is
[Note : [k] denotes the largest integer less than or equal to k]
1) 0
2) 1
3) 2
4) 3
5) 4
6) 5
7) 6
8) 7
9) 8
10) 9

28. Let k be a positive real number and let

If det (adj A) + det(adj B) = 106, then [k] is equal to

[Note : adj M denotes the adjoint of a square matrix M and [k] denotes the largest integer less than or
equal to k]
1) 0
2) 1
3) 2
4) 3
5) 4
6) 5
7) 6
8) 7
9) 8
10) 9

29. Consider a triangle ABC and let a, b and c denote the lengths of the sides opposite to vertices A, B
and C respectively. Suppose a = 6, b = 10 and the area of the triangle is 153. If ACB is obtuse and
if r denotes the radius of the incircle of the triangle, then r 2 is equal to
1) 0
2) 1
3) 2
4) 3
5) 4
6) 5
7) 6
8) 7
9) 8
10) 9
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 10) 9

30. Let a1, a2, a3,. ..., a11 be real numbers satisfying
a1 = 15, 27 2a2 > 0 and ak = 2ak 1 ak 2 for k = 3, 4,....., 11.

then the value of is equal to

1) 0
2) 1
3) 2
4) 3
5) 4
6) 5
7) 6
8) 7
9) 8
10) 9

Section-3
Paragraph Type
This section contains 2 paragraphs. Based upon each of the paragraphs 3 multiple choice questions have
to be answered. Each of these question has four choices (A), (B), (C) and (D) out of which ONLY ONE is
correct.
Directions for question 31 to 33 :
Tangents are drawn from the point P(3, 4) to the ellipse (x2/9) + (y2/4) = 1 touching the ellipse at
points A and B.
31. The coordinates of A and B are
1) (3, 0) and (0, 2)
2)

3)

4)

32. The orthocentre of the triangle PAB is

1) (5, 8/7)
2) (7/5, 25/8)
3) (11/5, 8/5)
4) (8/25, 7/5)

33. The equation of the locus of the point whose distances from the point P and the line AB are equal, is
1) 9x2 + y2 6xy 54x 62y + 241 = 0
2) x2 + 9y2 + 6xy 54x + 62y 241 = 0
3) 9x2 + 9y2 6xy 54x 62y 241 = 0

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 4) x2 + y2 2xy + 27x + 31y 120 = 0

Directions for question 34 to 36 :

Consider the polynomial f(x) = 1 + 2x + 3x2 + 4x3. Let s be the sum of all distinct real roots of f(x) = 0
and let t = |s|.
34. The real number s lies in the interval
1) (-(1/4), 0)
2) (-11, -(3/4))
3) (-(3/4), -(1/2))
4) (0, 1/4)

35. The area bounded by the curve y = f(x) and the lines x = 0, y = 0 and x = t, lies in the interval
1) (3/4, 3)
2) (21/64, 11/16)
3) (9, 10)
4) (0, 21/64)

36. The function f(x) is

1) Increasing in (-t, -(1/4)) and decreasing in (-(1/4), t)
2) Decreasing in (-t, -(1/4)) and increasing in (-(1/4), t)
3) Increasing in (t, t)
4) Decreasing in (t, t)

Section-4
Matrix Type
This Section contains 2 questions. Each question has four statements (A, B, C and D) given in Column I
and five statements (p, q, r, s and t) in Column II. Any given statement in Column I can have correct
matching with one or more statement(s) given in Column II. For example, if for a given question, statement
B matches with the statements given in q and r, then for that particular question, against statement B,
darken the bubbles corresponding to q and r in the ORS.
37. Match the statements in Column-I with the values in Column-II.
Column-I Column-II
A line from the origin meets the lines
and

A p -4
at P and Q

respectively. If length PQ = d, then d2 is

The values of x satisfying
B q 0
tan-1(x + 3) tan-1(x 3) = sin-1 (3/5) are
Non-zero vectors a, b and c satisfy a . b = 0,
C (b a) . (b + c) = 0 and 2 |b + c| = |b a|. r 4
If a = b + 4c, then the possible values of are
Let f be the function on [, ] given by
f(0) = 9 and f(x) = sin (9x/2) / sin(x/2)
D s 5
for x 0. The value of dx is

t 6
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 t 6

1) A-p
2) A-q
3) A-r
4) A-s
5) A-t
6) B-p
7) B-q
8) B-r
9) B-s
10) B-t
11) C-p
12) C-q
13) C-r
14) C-s
15) C-t
16) D-p
17) D-q
18) D-r
19) D-s
20) D-t

38. Match the statements in Column-I with those in Column-II.

[Note: Here z takes values in the complex plane and lm z and Re z denote, respectively, the imaginary
part and the real part of z.]
Column-I Column-II
The set of points z satisfying
A p An ellipse with eccentricity (4/5)
| z i | z || = | z + i | z || is contained in or equal to
The set of points z satisfying
B q The set of points z satisfying lm z = 0
| z + 4 | + | z 4 | = 10 is contained in or equal to
If |w| = 2, then the set of points
C r The set of points z satisfying |lm z| 1
z = w (1/w) is contained in or equal to
If |w| = 1, then the set of points
D s The set of points z satisfying |Re z| 2
z = w + (1/w) is contained in or equal to
t The set of points z satisfying |z| 3

1) A-p
2) A-q
3) A-r
4) A-s
5) A-t
6) B-p
7) B-q
8) B-r
9) B-s
10) B-t
11) C-p
12) C-q

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 13) C-r
14) C-s
15) C-t
16) D-p
17) D-q
18) D-r
19) D-s
20) D-t

Physics
Section-1
Single Correct Choice Type
This section contains 6 multiple choice questions. Each question has four choices (A), (B), (C) and (D) out
of which ONLY ONE is correct.
39. A biconvex lens of focal length 15 cm is in front of a plane mirror. The distance between the lens and
the mirror is 10 cm. A small object is kept at a distance of 30 cm from the lens. The final image is
1) Virtual and at a distance of 16 cm from the mirror
2) Real and at a distance of 16 cm from the mirror
3) Virtual and at a distance of 20 cm from the mirror
4) Real and at a distance of 20 cm from the mirror

40. A uniformly charged thin spherical shell of radius R carries uniform surface charge density ofper
unit area. It is made of two hemispherical shells, held together by pressing them with force F (see
figure). F is proportional to

1) (1/ 0) 2R2
2) (1/ 0) 2R

3) (1/ 0) (2/R)

4) (1/ 0) (2/R2)

41. A hollow pipe of length 0.8 m is closed at one end. At its open end a 0.5 m long uniform string is
vibrating in its second harmonic and it resonates with the fundamental frequency of the pipe. If the
tension in the wire is 50 N and the speed of sound is 320 ms1, the mass of the string is
1) 5 grams
2) 10 grams
3) 20 grams
4) 40 grams

42. A Vernier calipers has 1 mm marks on the main scale. It has 20 equal divisions on the Vernier scale
which match with 16 main scale divisions. For this Vernier calipers, the least count is
1) 0.02 mm
2) 0.05 mm

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 3) 0.1 mm
4) 0.2 mm

43. A block of mass 2 kg is free to move along the x-axis. It is at rest and from t = 0 onwards it is
subjected to a time-dependent force F(t) in the x direction. The fore F(t) varies with t as shown in the
figure. The kinetic energy of the block after 4.5 seconds is

1) 4.50 J
2) 7.50 J
3) 5.06 J
4) 14.06 J

44. A tiny spherical oil drop carrying a net charge q is balanced in still air with a vertical uniform electric
field of strength (81/7) 10 5 Vm -1. When the field is switched off, the drop is observed to fall with
terminal velocity 2 103 ms1. Given g = 9.8 ms2, viscosity of the air = 1.8 105 Ns m 2 and the
density of oil = 900 kg m 3, the magnitude of q is
1) 1.6 1019 C
2) 3.2 1019 C
3) 4.8 1019 C
4) 8.0 1019 C

Section-2
Integer Type
This section contains 5 questions. The answer to each of the questions is a single-digit integer, ranging
from 0 to 9. The correct digit below the question number in the ORS is to be bubbled.
45. Image of an object approaching a convex mirror of radius of curvature 20 m along its optical axis is
observed to move from (25/3) m to (50/7) m in 30 seconds. What is the speed of the object in km per
hour ?
1) 0
2) 1
3) 2
4) 3
5) 4
6) 5
7) 6
8) 7
9) 8
10) 9

46. A diatomic ideal gas is compressed adiabatically to (1/32) of its initial volume. If the initial temperature

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 of the gas is T i (in kelvin) and the final temperature is aT i, the value of a is
1) 0
2) 1
3) 2
4) 3
5) 4
6) 5
7) 6
8) 7
9) 8
10) 9

47. To determine the half life of a radioactive element, a student plots a graph of |dN(t)/dt| versus t. Here
(dN(t)/dt) is the rate of radioactive decay at time t. If the number of radioactive nuclei of this element
decreases by a factor of p after 4.16 years, the value of p is

1) 0
2) 1
3) 2
4) 3
5) 4
6) 5
7) 6
8) 7
9) 8
10) 9

48. At time t = 0, a battery of 10 V is connected across points A and B in the given circuit. If the capacitors
have no charge initially, at what time (in seconds) does the voltage across them become 4 V?
[Take : ln 5 = 1.6, ln 3 = 1.1]

1) 0
2) 1
3) 2
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 4) 3
5) 4
6) 5
7) 6
8) 7
9) 8
10) 9

49. A large glass slab ( = 5/3) of thickness 8 cm is placed over a point source of light on a plane surface.
It is seen that light emerges out of the top surface of the slab from a circular area of radius R cm.
What is the value of R?
1) 0
2) 1
3) 2
4) 3
5) 4
6) 5
7) 6
8) 7
9) 8
10) 9

Section-3
Paragraph Type
This section contains 2 paragraphs. Based upon each of the paragraphs 3 multiple choice questions have
to be answered. Each of these questions has four choices (A), (B), (C) and (D) out of which ONLY ONE is
correct.
Directions for question 50 to 52 :
The key feature of Bohrs theory of spectrum of hydrogen atom is the quantization of angular
momentum when an electron is revolving around a proton. We will extend this to a general rotational
motion to find quantized rotational energy of a diatomic molecule assuming it to be rigid. The rule to
be applied is Bohrs quantization condition.
50. A diatomic molecule has moment of inertia l. By Bohrs quantization condition its rotational energy in
the nth level (n = 0 is not allowed) is
1) (1/n2) (h2/82l)
2) (1/n) (h2/82l)
3) n (h2/82l)
4) n2 (h2/82l)

51. It is found that the excitation frequency from ground to the first excited state of rotation for the CO
molecule is close to (4/) 10 11 Hz. Then the moment of inertia of CO molecule about its centre of
mass is close to (Take h = 2 1034 J s)
1) 2.76 1046 kg m 2
2) 1.87 1046 kg m 2
3) 4.67 1047 kg m 2
4) 1.17 1047 kg m 2

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52. In a CO molecule, the distance between C (mass = 12 a.m.u.) and O (mass = 16 a.m.u.), where 1
a.m.u. = (5/3) 10-27 kg, is close to
1) 2.4 1010 m
2) 1.9 1010 m
3) 1.3 1010 m
4) 4.4 1011 m

Directions for question 53 to 55 :

When liquid medicine of density is to be put in the eye, it is done with the help of a dropper. As the
bulb on the top of the dropper is pressed, a drop forms at the opening of the dropper. We wish to
estimate the size of the drop. We first assume that the drop formed at the opening is spherical
because that requires a minimum increase in its surface energy. To determine the size, we calculate
the net vertical force due to the surface tension T when the radius of the drop is R. When this force
becomes smaller than the weight of the drop, the drop gets detached from the dropper.
53. If the radius of the opening of the dropper is r, the vertical force due to the surface tension on the drop
of radius R(assuming r << R) is
1) 2rT
2) 2RT
3) 2r2T/R
4) 2r2T/r

54. If r = 5 104 m, = 103 kgm 3, g = 10 ms2, T = 0.11 Nm 1, the radius of the drop when it detaches
from the dropper is approximately
1) 1.4 103 m
2) 3.3 103 m
3) 2.0 103 m
4) 4.1 103 m

55. After the drop detaches, its surface energy is

1) 1.4 106 J
2) 2.7 106 J
3) 5.4 106 J
4) 8.1 106 J

Section-4
Matrix Type
This section contains 2 questions. Each Question has four statements (A, B, C and D) given in Column I
and five statements (p, q, r, s and t) in Column II. Any given statement in Column I can have correct
matching with one or more statement(s) given in Column II. For example, if for a given question, statement
B matches with the statements given in q are r, then for that particular question, against statement B,
darken the bubble corresponding to q and r in the ORS.
56. You are given many resistances, capacitors and inductors. These are connected to a variable DC
voltage source (the first two circuits) or an AC voltage source of 50 Hz frequency (the next three
circuits) in different ways as shown in Column II. When a current I (steady state for DC or rms for AC)
flows through the circuit, the corresponding voltage V1 and V2. (indicated in circuits) are related as
shown in Column I.
Column I Column II

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A I 0, V1 is proportional to I p

B I 0, V2 > V1 q

C V1 = 0, V2 = V r

D I 0, V2 is proportional to I s

1) A-p
2) A-q
3) A-r
4) A-s
5) A-t
6) B-p
7) B-q
8) B-r
9) B-s
10) B-t
11) C-p
12) C-q
13) C-r
14) C-s
15) C-t
16) D-p
17) D-q
18) D-r
19) D-s
20) D-t

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57. Two transparent media of refractive indices 1 and 3 have a solid lens shaped transparent material
of refractive index 2 between them as shown in figures in Column II. A ray traversing these media is
also shown in figures. In Column I different relationships between
1 , 2 and 3 are given. Match
them to the ray diagrams shown in Column II.
Column I Column II

A 1 < 2 p

B 1 > 2 q

C 2 = 3 r

D 2 > 3 s

1) A-p
2) A-q
3) A-r
4) A-s
5) A-t
6) B-p
7) B-q
8) B-r
9) B-s
10) B-t
11) C-p
12) C-q
13) C-r
14) C-s
15) C-t
16) D-p
17) D-q
18) D-r
19) D-s
20) D-t

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 Answer Key

1) 3 2) 1 3) 4 4) 2 5) 3 6) 4 7) 3 8) 7 9) 3 10) 4
11) 8 12) 2 13) 3 14) 2 15) 2 16) 1 17) 4 18) 1,4,6,7,8,10,11,12,16 19) 3,4,10,11,12,18 20) 2
21) 3 22) 4 23) 4 24) 1 25) 2 26) 2 27) 4 28) 5 29) 4 30) 1
31) 4 32) 3 33) 1 34) 3 35) 1 36) 2 37) 5,6,8,12,18 38) 2,3,6,11,14,15,17,18,19,20 39) 2 40) 1
41) 2 42) 4 43) 3 44) 4 45) 4 46) 5 47) 9 48) 3 49) 3 50) 4
51) 2 52) 3 53) 3 54) 1 55) 2 56) 3,4,5,7,8,9,10,11,12,17,18,19,20 57) 1,3,7,9,10,11,13,15,17,19

1/1 eng.edooni.com
 Prepared by Aneesh Damodaran
IONIC CRYSTALS

1) In the following diagram, the circles filled with black color represent the cations, whereas the big
circles represent the anions.

which of the following is the correct statement relating to above diagrams

1) The cation in diagram A is unstable.
2) The cation in diagram B is stable.
3) The cations in both the diagrams A & B are stable.
4) All
Note: The state of the atom or ion occupying any void in a crystal lattice is stable only when it is touching the surround-
ing atoms or ions.
2) Match the following
Limiting radius ratio Geometry
A) 0.155 - 0.225 1) Tetrahedral
B) 0.225 - 0.414 2) Octahedral
C) 0.414 - 0.732 3) Trigonal
D) 0.732-0.999 4) Body centred cubic
The correct matching is
A B C D
1) 1 3 2 4
2) 3 2 4 1
3) 3 1 2 4
4) 1 2 4 3
3) Match the following
Co-ordination number Limiting radius ratio
A)3 1) 0.155-0.225
B) 4 2) 0.225-0.414
C) 8 3) 0.414-0.732
D) 6 4) 0.732-0.999
Correct matching is
A B C D
1) 1 2 3 4
2) 1 2 4 3
3) 1 3 2 4
4) 2 3 4 1
4) The limiting radius ratio for an ionic compound AB is 0.427. The smaller cation A+ will be more
stable when it occupies
1) Tetrahedral voids 2) Octahedral voids 3) Trigonal voids 4) Body centred cubic voids
Note: The cation can touch the anions when it occupies trigonl or tetrahedral voids, but it will be more stable in octahedral
void as it is surrounded by more number of anions. It will be less stable in body centred cubic void, even though it is
surrounded by even more anions, as it cannot touch the anions
5) The Cl- ions are arranged in expanded cubic close packing in NaCl crystal. The radii of Na+ and
Cl- ions are 95pm and 181 pm respectively. The type of voids occupied by Na+ ions is
1) Octahedral 2) Tetrahedral 3) Trigonal 4) All
r
Na
Hint: r 0.5248
Cl

6) The crystal structure present in NaCl is called

1) Fluorite structure 2) Rock-salt structure 3) Anti-fluorite structure 4) Spinel structure
Note : In Rock-salt structure, the bigger anions occupy the lattice points of expanded face centred cubic lattice. The
smaller cations occupy all the octahedral holes. The limiting radius ratio is in between 0.414 and 0.732. The co-ordination
numbers cation and anion are (6:6). The general formula of ionic compounds having this structure is AB.
Examples : NaCl, KCl, MgO, CaO, SrO etc.,

7) The number of NaCl units present in a single unit cell of NaCl crystal is
1) 1 2) 2 3) 4 4) 6
+
8) The number of octahedral holes occupied by Na ions in a single unit cell of NaCl is
1) 4 2) 8 3) 2 4) Zero
9) Which of the following does not crystallise in the rock salt structure
1) NaCl 2) KCl 3) CsCl 4) MgO
Note : Usually halides of Cesium assume BCC structures as the limiting radius ratio is greater than 0.732
10) The number of nearest Cl- ions around an Na+ ion in NaCl crystal is
1) 8 2) 6 3) 4 4) 12
- -
11) The number of nearest Cl ions arround a Cl ion in NaCl crystal is
1) 8 2) 6 3) 4 4) 12
+ -
12) The radii of Na and Cl ions are 95 pm and 181 pm respectively. The edge length of unit cell in
NaCl is
1) 457 pm 2) 552 pm 3) 190 pm 4) 362 pm
Note : edge length in NaCl = 2rc+ 2ra
13) The crystal structure present in CsCl is referred to as
1) FCC 2) BCC 3) HCP 4) None
Note : BCC structure is present when the limiting radius ratio isgreater than 0.732. The anions occupy the lattice points
of simple cubic lattice. The cations occcupy centred cubic voids. This structure can be considered as interpenetrating
primitive cubic lattices of cation and anion.
The co-ordination numbers are (8:8). The number of formula units present per a single unit cell is one (one cation and
one anion). The general formula is AB.
Examples : CsCl, CsBr, CsI, CsCN, TlCl, TlBr, TlI, TlCN etc.,

14) The number of nearest Cl- ions present around a Cs+ ions in CsCl crystal is
1) 6 2) 8 3) 12 4) 4
15) The number of nearest Cs+ ions present around a Cs+ ion in CsCl crystal is
1) 8 2) 6 3) 4 4) 12
 Hint : If only Cs+ ions are considered they occupy lattice points of primitive cubic lattice
16) The number of second nearest Cs+ ions present around a Cs+ ion in CsCl is
1) 4 2) 8 3) 12 4) 6
+ -
17) The radii of Cs and Cl ions are 1.69 and 1.81 respectively. The edge length of the unit cell
in CsCl will be
1) 7 2) 3.38 3) 4.04 4) 3.5
Hint : In BCC, the ions touch along the body diagonal
Length of body diagonal = 2rc+2ra = 3a
18) The ionic compound which crystallises in anti-fluorite structure is
1) NaCl 2) Na2O 3) CaF2 4) Al2O3
Note : In the anti-fluorite structure, anions are arranged in cubic closest packing and cations occupy all the tetrahedral
voids. There are four anions and eight cations per unit cell of this structure and hence, the general formula of an ionic
compound is A8B4 or A2B.
The ideal radius ratio is between 0.225 - 0.414. But this ratio is not always maintained.The co-ordination numbers of
cation and anion are (4:8).
Examples : Na2O, K2O, Li2O, Rb2O, K2S, Cl2O, Na2S etc.,

19) In a unit cell of an ionic crystal, anions (Y) occupy the lattice points of face centred cubic lattice
and cations (X) occupy all the tetrahedral voids. The formula of the ionic compound will be
1) XY2 2) X2Y2 3) X2Y 4) XY
20) The number of anions per a single unit cell in antifluorite structure is
1) 2 2) 4 3) 8 4) 1
21) The type of voids occupied by cations in antifluorite structure is
1) Octahedral 2) Tetrahedral 3) Trigonal 4) Body centred cubic
22) The co-ordination number of Na+ ions in Na2O is
1) 2 2) 4 3) 8 4) None
2-
23) The type of voids occupied by O ions in Na2O crystal is
1) Tetrahedral 2) Octahedral 3) Body centred cubic 4) Trigonal
+
24) The number of Na ions present per a single unit cell in Na2O crystal is
1) 4 2) 2 3) 8 4) 12
25) The fluorite crystal structure is present in
1) NaF 2) CaF2 3) AlF3 4) CsF
Note : In the fluroite structure, the cations are arranged into cubic close packing and the anions occupy all the tetrahedral
voids. Thus there are four cations and eight anions per a unit cell. Hence the formula of ionic compound is A4B8 or AB2.
The co-ordination numbers of cation and anion are (8:4).
Examples : CaF2, ZrO2, UO2, ThO2, BaF2, BaCl2, SrCl2, PbCl2 etc.,
26) The number of anions per a single unit cell in fluorite structure is
1) 2 2) 4 3) 8 4) 1
27) The type of voids occupied by anions in fluorite structure is
1) Octahedral 2) Tetrahedral 3) Trigonal 4) Body centred cubic
28) The co-ordination number of Ca2+ ions in CaF2 is
1) 2 2) 4 3) 8 4) None
29) The type of voids occupied by Ca2+ ions in CaF2 crystal is
1) Tetrahedral 2) Octahedral 3) Body centred cubic 4) Trigonal
2+
30) The number of Ca ions present per a single unit cell in CaF2 crystal is
1) 4 2) 2 3) 8 4) 12
2+ -
31) The radii of Ca and F ions respectively are 100 pm and 131 pm. The edge length of the unit
cell in CaF2 is
1) 231 pm 2) 533.5 pm 3) 462 pm 4) 362.5 pm
Hint: The Fluoride ions are present along the body diagonal at one fourth distance from the corner of the cube. Hence the
distance between calcium and fluoride ions is 1/4th of length of body diagonal.
32) The substance containing zinc-blende crystal structure is
1) NaCl 2) ZnCl2 3) BeO 4) CsCl
Note: In zinc-blende or sphalerite structure, anions occupy the face centred cubic lattice points and cations occupy half of
the tetrahedral holes (of one type). The ideal radius ratio is in between 0.225 to 0.414. There are four anions and four
cations in the unit cell. Therefore the formula is A4B4 or AB. The co-ordination numbers of cation and anion are (4:4).
Examples: ZnS, BeO etc.,

33) The number of anions per a single unit cell in zinc-blende structure is
1) 2 2) 4 3) 8 4) 1
34) The type of voids occupied by cations in zinc-blende structure is
1) Octahedral 2) Tetrahedral 3) Trigonal 4) Body centred cubic
35) The co-ordination number of Zn2+ ions in ZnS is
1) 2 2) 4 3) 8 4) None
36) The type of voids occupied by S2- ions in ZnS crystal is
1) Tetrahedral 2) Octahedral 3) Body centred cubic 4) Trigonal
2+
37) The number of Zn ions present per a single unit cell in ZnS crystal is
1) 4 2) 2 3) 8 4) 12
2-
38) The co-ordination number of S ions in ZnS is
1) 2 2) 4 3) 8 4) None
39) The compound containing spinel structure is
1) MgAl2O4 2) Fe2O3 3) ThO2 4) KCl
Note: In spinel structure, the oxide ions are arranged in cubical closest packing and one eighth of the tetrahedral holes are
occupied by divalent metal ion (A2+) and one half of the octahedral holes are occupied by trivalent metal ions (B3+). Thus
in a unit cell there are four oxide ions, one divalent metal ion(A2+) and two trivalent metal ions (B3+). The general formula
of the compound is AB2O4.
Examples: MgAl2O4,ZnAl2O4, ZnFe2O4 etc.,
40) The crystal structure present in Al2O3 is called as
1) corundum structure 2) spinel structure 3) rock-salt structure 4) Fluorite structure
Note: In the corundum structure, anions form hexagonal closest packing and cations are present in 2/3 of the octahedral
holes. The general formula of the compound is M2O3.
Examples: Fe2O3, Al2O3, Cr2O3 etc.,
41) Inverse spinel structure is found in
1) Chromite 2) Magnetite 3) Spinel 4) Corundum

KEY
1) 3 2) 3 3) 2 4) 2 5) 1 6) 2 7) 3 8) 1 9) 3 10) 2 11) 4 12) 2
13) 2 14) 2 15) 2 16) 3 17) 3 18) 2 19) 3 20) 2 21) 2 22) 2 23) 3 24) 3
25) 2 26) 3 27) 2 28) 3 29) 3 30) 1 31)2 32) 3 33) 2 34) 2 35) 2 36) 1
37) 1 38) 3 39) 1 40) 1 41) 2
 METALLURGY
IIT-JEE

DISTRIBUTION OF ELEMENTS ON EARTH

1) The most abundant element in the universe is
1) He 2) O 3) C 4) H
2) The core of the earth consists of
1) SiO2 2) Al 3) Fe alloyed with Ni 4) Fe in oxidised form
3) Light rocks in the continental crust contain
1) SiO2 2) Al2O3 + SiO2 3) MgO + SiO2 4) Al2O3
Note : Heavy rocks contain MgO + SiO2
4) The first four most abundant elements in the earth crust are respectively are
1) O, Si, Al, Fe 2) O, C, H, N 3) O, Si, Al, Ca 4) O, Si, Na, Al
5) The second most abundant element in heavy rocks is
1) Al 2) Mg 3) Fe 4) Si
6) The percentage by weight of oxygen and silicon in the earth crust is
1) 75% 2) 50% 3) 25% 4) 85%
7) Granite is an example of
1) Sedimentary rocks 2) Igneous rocks 3) Heavy rocks 4) None
Note : Granite is mainly aluminosilicate. It is formed on cooling of magma ( it is an igneous light rock)
8) The number of elements found in the nature is
1) 100 2) 120 3) 56 4) 88
9) Sea weeds are an important source of
1) Chlorine 2) Fluorine 3) Bromine 4) Iodine
10) Sea cucumbers are enriched with
1) Iodine 2) Vanadium 3) Bromine 4) None
11) The element present in the enzyme, carbonic anhydrase is
1) Zinc 2) Copper 3) Silver 4) Cadmium
12) The major source of bromine is
1) Horn silver 2) Sea water 3) Galena 4) All
13) The elements which can be recovered on large scale from sea water are
1) Na, Cl, Mg & Br 2) Na, Mg, Al & Li 3) Na, Cl, Fe & C 4) Zn, Cu, Mg & Al
14) The metals which exist in their native state in nature are
1) Cu, Ag, Au & Pt 2) Fe, Zn, Hg & Ni 3) Cu, Ag, Fe & Na 4) Na, Mg, Al & Si
15) O, N and Ar belong to the category
1) Chalcophiles 2) Lithophiles 3) Atmophiles 4) None

ORES
1) The characteristics of an ore is/are
1) high percentage of metal 2) low amounts of easily removable impurities
3) Low expenditure needed for the exraction 4) All
2) Which one of the following is not an oxide ore ?
1) Bauxite 2) Cuprite 3) Magnetite 4) Iron pyrites
Note : Bauxite Al2O3. 2H2O
Cuprite Cu2O
Magnetite Fe3O 4
Iron pyrites FeS2
3) Which one of the following is not an ore of iron
1) Magnetite 2) Hematite 3) Siderite 4) Cassiterite
 Note : Hematite - Fe2O 3
Siderite - FeCO 3
Cassiterite - SnO2
4) The ore which does not contain Zinc is
1) Zinc blende 2) Zincite 3) Calamine 4) Zircon
Note : Zincite - ZnO
Zinc blend - ZnS
Calamine - ZnCO3
Zircon - ZrSiO4
5) Match the following
A) Malachite 1) AgCl
B) Horn Silver 2) PbSO4
C) Anglesite 3) Cr2O3. FeO
D) Chromite 4) CuCO3.Cu(OH)2
The correct Matching is
A B C D
1) 4 1 3 2
2) 4 1 2 3
3) 2 1 4 3
4) 3 1 2 4
6) The phosphate ore of calcium is
1) Dolomite 2) Barytes 3) Monite 4) Argentite
Note : Dolomite : CaCO3. MgCO3
Barytes : BaSO4
Monite : Ca3 (PO4)3. H2O
Argentite : Ag2S
7) Which among the following is a sulphide ore of copper
1) Malachite 2) Azurite 3) Copper pyrites 4) Cuprite
Note : Malachite - CuCO3 . Cu(OH)2
Azurite - [2 CuCO3]. Cu(OH)2
Copper pyrites - Cu2S. Fe2S3
Cuprite - Cu2O
8) The silicate mineral of Thorium is
1) Thorite 2) Monazite 3) Cryolite 4) None
Note : Thorite - ThSiO4
Monazite - Phosphate mineral of Thorium and other rare earths
Cryolite - Na3AlF6
9) Galena is the mineral of
1) Zn 2) Pb 3) Pd 4) Ni
Note : Galena - PbS
10) The element(s) that may occur in the native form in the nature is
1) Gold 2) Silver 3) Copper 4) All
11) The mineral which does not contain fluorine as one of the constituent element is
1) Cryolite 2) Fluorite 3) Both 1 & 2 4) None
Note : Cryolite - Na3AlF6
Fluorite - CaF2
12) Match the following
A) Cerussite 1) MgSO4. 7H2O
B) Copper glance 2) 3Fe2O3. 3H2O
C) Limonite 3) Cu2S
D) Epsomite 4) PbCO3
 The correct matching is
A B C D
1) 1 2 4 3
2) 4 3 2 1
3) 2 4 3 1
4) 4 3 1 2
13) The chemical composition of wulfenite is
1) CuCO3. Cu(OH)2 2) PbMnO4 3) WO3 4) TiO2
14) The chemical composition of ruby copper is
1) Cu2O 2) Cu2S 3) CuCO3 4) Cu (OH)2
15) The ore of mercury is
1) Cinnabar 2) Fluorspar 3) Phosphorite 4) Argentite
Note : Cinnabar - HgS
16) The chemical composition of pyrolusite is
1) PbSO4 2) MnO2 3) PbS 4) Al2O3
17) Pitch blend is the chief ore of
1) Palladium 2) Lead 3) Uranium 4) Cesium
Note : Pitch blend - U3O8
18) The silicate ore of zinc is
1) Zinc blend 2) Willemite 3) Mica 4) Zincite
Note : Willemite - Zn2SiO4
19) The chemical composition of chile salt petre is
1) KNO3 2) NaNO3 3) AgNO3 4) Fe2O3
Note : KNO3 - Indian salt peter
NaNO3 - Chile salt peter
20) The composition of spathic iron ore is
1) Fe2S 2) FeS2 3) FeCO3 4) None
Note : Sideritic or spathic iron ore - FeCO3
21) Match the following
A) CaMg3 (SiO3)4 1) Pentlandite
B) KCl. MgCl2. 6H2O 2) Carnallite
C) (Ni, Fe) S 3) Asbestos
D) TiO2 4) Rutile
The correct matching is
A B C D
1) 3 2 1 4
2) 1 2 3 4
3) 3 2 4 1
4) 4 2 1 3
22) The chemical composition of ruby silver is
1) AgCl 2) Ag3SbS3 3) Ag2S 4) AgCO3
23) The sulfide ore of copper which does not contain iron is
1) Copper pyrites 2) Cuprite 3) Chalcocite 4) Cobaltite
Note : Chalcosite - Cu2S
Cobaltite - CoAsS
24) Wolframite and Scheelite are the ores of
1) Zinc 2) Manganese 3) Tungsten 4) Gold
Note : Wolframite - (Fe, Mn) WO4
Scheelite - CaWO4
25) The silicate form of beryllium is
1) Beryl 2) Emerald 3) Aquamarine 4) All
 Note : Beryl is the silicate ore of beryllium (Be3Al2 (SiO3)6)
Emerald and Aquamarine are the gemstone varieties of beryl.
Emerald - Green colored due to presence of chromium
Aquamarine - Transparent variety of beryl with a delicate blue color.
26) The chemical composition of sphalerite is
1) ZnS 2) MnS 3) ZnSO4 4) NaCl
Note : ZnS is also called as Zincblend.
27) Ruby and sapphire are the gemstone varieties of
1) Bauxite 2) Corundum 3) Gibbsite 4) Gold
28) The stone which floats on water is
1) Sand stone 2) Pumice 3) Topaz 4) Hyacinth
29) Cooperite is the ore containing
1) Pt 2) Pd 3) Ni 4) All
Note : Cooperite - (Pt, Pd, Ni) S
30) The mineral containing Lithium is
1) Spodumene 2) Lepidolite 3) Petalite 4) All
Note : Spodumene - LiAl (SiO3)2 - (an inoslilicate)
Lepidolite - K Li2Al (Al, Si)3O10(F, OH)2 - (A phyllosilicate)
Petalite - LiAlSi4O10 (a tecto silicate)
31) The formula of stibnite (antimonite) is
1) SbS2 2) Sb2S 3) Sb2S3 4) Sb2S5

ORE DRESSING
1) Choose the incorrect statement
i) The rocky, sandy and siliceous impurities associated with minerals are called gangue
ii) Flux is the chemical substance that reacts with infusible gangue by forming a fusible mass
called slag.
iii) The density of slag is less than that of metal
iv) All minerals are ores.
The correct statement (s)
1) i & iii 2) i only 3) iv only 4) iii & iv
2) The chemical composition of Thomas slag, used as a fertilizer, is
1) CaSO4. 2H2O 2) Ca3(PO4)2 3) Ca(NO3)2 4) CaSiO3
3) The basic flux used to remove SiO2 is
1) Al2O3 2) CaO 3) MgCl2 4) None
Note : SiO 2 + CaO CaSiO3
Acidic gangue basic flux slag
4) Which of the following ore concentration methods depends upon difference in specific gravity of
the ore particles and impurities
1) Levigation method 2) Washing method 3) Wilfley method 4) All
5) The ore which can be concentrated by liquation method is
1) Stibnite 2) Heamatite 3) Magnesite 4) All
6) The ore cassiterite is concentrated by
1) Magnetic method 2) Liquation 3) Froath floatation 4) Wilfley method
7) The separation of magnetite (Fe3O4), Chromite (Cr2O3. FeO) and pyrolusite (MnO2) ores
from the non magnetic gangue is usually done by
1) Leaching 2) Magnetic separation 3) Liquation 4) None
8) The magnetic impurity present in cassiterite (SnO)2 is
1) Wolframite 2) Bauxite 3) Galena 4) Willemite
9) The usual technique employed in separation of gangue from hydrophobic sulfide ores is
1) Froth floatation 2) Leaching 3) Roasting 4) Levigation
10) Choose the correct statement related to froth flotation process
a) Collectors like potassium ethyl xanthate are used to enhance the non wettability
(hydrophobicity) of mineral particles.
b) Pine oil is used as frother, which helps in formation of froth
c) Froth is stabilised by adding froth stabilizers like aniline or cresol
d) The gangue particles are more hydrophilic than ore particles and sink to the bottom
The correct statement (s)
1) a & c 2) a only 3) c & d 4) All
H
11) The modifier used to increase the p during froth flotation process is
1) Soda ash 2) Lime 3) H2SO4 4) 1 or 2
12) The depressant used to suppress the floating of galena is
1) Lime 2) Soda ash 3) NaCN 4) All
13) The depressant used to prevent ZnS to form froth is
1) Soda ash 2) NaCN 3) Aniline 4) None
Note : NaCN forms a layer of Na2[Zn(CN)4] on the surface of ZnS particle and thus by preventing if from the ormation of
froth.
ZnS + NaCN Na2[Zn(CN)4] + Na2S
This technique is used to separate Galena - PbS (which forms froth selectively) from ZnS particles
14) The separation of ore by converting it into a water soluble compound by reacting with a suitable
chemical subtance is called
1) Roasting 2) Leaching 3) Liquation 4) Smelting
15) In the Bayers process, the leaching of alumina is done by using
1) Na2CO3 2) NaOH 3) SiO2 4) CaO
Note : Alumina is converted to water soluble sodium meta aluminate by treating with sodium hydroxide
Al2O3 + 2NaOH 2NaAlO2 + H2O
(or)
2 Al2O3 (s) + 2OH- (aq) + 3H2O 2[Al(OH)4]- (aq)
16) The leaching agent used in concentration of argentite ore is
1) NaCN 2) NaCN + O2 3) NaOH 4) O2
Hint : Ag2S + 4NaCN + 2O2 2Na[Ag(CN)2] + Na2SO4
Soluble complex
17) Cupric oxide can be leached by using
1) NaOH 2) NaCN 3) H2SO4 4) O2
Hint : CuO + H2SO4 CuSO4 + H2O
water soluble

EXTRACTION OF CRUDE METAL FROM THE ORE

1) The process of removal of carbon dioxide by heating calamine ore is called
1) Roasting 2) Smelting 3) Calcination 4) All
ZnO CO2
Note : ZnCO3
2) The ore which is converted to its oxide by calcination process is
1) Cuprite 2) Magnesite 3) Heamatite 4) All
3) The gas evolved during the roasting of sulfide ores is
1) H2S 2) SO3 3) O2 4) SO2
Example : 4FeS2 + 11O2 2 Fe2O3 + 8SO2
4) The reaction which can occur during the roasting of zinc blend at 6500C is
1) 2 ZnS + 3O2 2 ZnO + 2 SO2 2) ZnS + 2O2 ZnSO4
3) Both 1 & 2 4) None
5) During the chloridizing roasting, silver glance is converted to
1) Ag2S 2) AgCl 3) AgNO3 4) Ag
 0
Note : 600 C
Ag2S + 2 NaCl + 2O2
2 AgCl + Na2SO4
6) Choose the correct statement
a) The free energies of formation ( f G 0 ) of sulphide ores are greater than those of CS2 and
H2S. Hence the reduction of sulfide ores by carbon and hydrogen is not thermodynamically feasible.
b) The heat efficiency of reverberatory furnace is very high.
c) The heat efficiency of blast furnace is very low.
d) The least temperature in the blast furnace is observed at the top.
Correct statement are
1) a only 2) a & d 3) b & c 4) d only
7) The reducing agent used in the reduction of zinc oxide is
1) H2 2) Coke 3) CaCO3 4) Water gas
8) The reducing agent used in the extraction of Nickel from its oxide is
1) Coke 2) Coal gas 3) Water gas 4) Nickel
9) Molydbenum can be extracted from its oxide by reducing with
1) H2 2) Coke 3) O2 4) None
10) The reducing agent used in Goldschmidt alumino thermic process is
1) Al2O3 2) Al 3) AlCl3 4) Fe
11) Chromium can be extracted from its oxide by using aluminium. In this case aluminium acts as
1) Reducing agent 2) Oxidising agent 3) Both 1 & 2 4) None
12) Alumina can be reduced to aluminium by
1) Coke 2) Electrolysis 3) H2 4) CO
Note: Aluminium cannot be obtained by chemical reduction due to its strong electro-positive nature and strong affinity with
oxygen.
13) The metal obtained during the reduction of cassiterite by coke is
1) Zinc 2) Antimony 3) Tin 4) Carbon
14) The reducing agent which can be used in the reduction of TiCl4 to Ti is
1) Coke 2) Mg 3) H2O 4) CO
15) During smelting process of copper pyrites, most of the iron impurity is removed as
1) Fe2O3 2) FeSiO3 3) FeS 4) FeSO4
Note : 2FeS + 3O2 2 FeO + 2SO2
FeO + SiO2 FeSiO3
16) The composition of matte obtained during smelting of copper pyrites is
1) Cu2O 2) Cu2S 3) Cu2S and little FeS 4) FeS and little Cu2S
Note :During the smelting process most of the iron sulfide is removed as FeSiO3 slag. Wheras copper remains mostly in sulfide
form (Cu2S).
17) The main reaction that occurs during the roasting of copper pyrites in a reverberatory furnace is
1) Cu2S. Fe2S3 + O2 Cu2S + 2 FeS + SO2
2) Cu2S. Fe2S3 + 6O2 Cu2O + Fe2O3 + 4SO2
3) CuFeS2 + 2O2 CuO + FeO + SO2
4) Cu2S. Fe2S3 Cu2S + Fe2S + 2S
18) Choose the incorrect statement
1) Silica is used as flux to remove iron part from copper pyrites.
2) Blister copper is formed due to auto reduction of Cu2O in the bessemerization process.
3) Pure copper is formed at anode during electrolytic refining of blister copper.
4) Coke is used to produce enough heat to drive the smelting process of copper pyrites.
19) The reducing agent used in Belgian process during the extraction of Zinc is
1) ZnO 2) C 3) CO2 4) ZnS
20) Which of the following reaction represents roasting of sphalerite ore ?
1) 2Cu2S + 3O2 2Cu2O + 2SO2 2) ZnS + O2 ZnO + SO2
 3) ZnO + C Zu + CO 4) Ag2S + NaCN + O2 Na[Ag(CN)2]
21) The charge feed into the blast furnace during the extraction of cast iron is
1) 8:4:1 parts by weight of roasted ore, coke and silica
2) 8:4:1 parts by weight of roasted ore, coke and lime stone
3) 8:4:1 parts by weight of roasted ore, silica and lime stone
4) 8:4 parts by weight of roasted ore and lime stone
22) The reaction that occurs in the zone of heat absorption in the blast furnace during the extraction of
cast iron is
1) Fe2O3 + 3C 2Fe + 3CO 2) Fe2O3 + 3CO 2Fe + 3CO2
3) CaO + SiO2 CaSiO3 4) both 1 and 2
23) The reaction that does not occur in the zone of reduction in the blast furnace during the extraction of
cast iron is
1) Fe2O3 + 3C 2Fe + 3CO 2) Fe2O3 + 3CO 2Fe + 3CO2
3) CaCO3 CaO + CO2 4) both 1 and 2
24) The endothermic reaction that occurs in the zone of heat absorption in the blast furnace during the
extraction of cast iron is
1) CO2 + C 2CO 2) CaCO3 CaO + CO2
3) C + O2 CO2 4) both 1 and 2
25) Silica present as impurity in iron ore is removed as slag by reacting with
1) CaO 2) C 3) CO 4) all
26) The temperature of zone of fusion in the blast furnace is in the range of
1) 8000C - 10000C 2) 4000C - 7000C 3) 12000C - 13000C 4) 13000C - 15000C
27) Combustion of coke and melting of iron occurs in the following region of blast furnace
1) Zone of reduction 2) Zone of heat absorption 3) Zone of fusion 4) None
28) The percentage of carbon in cast iron is
1) 4% 2) 0.2% 3) 2% 4) 0.4%
29) The percentage of carbon in wrought iron is
1) 4% 2) 0.2% 3) 2% 4) 0.4%
30) The Puddlers candles are produced due to burning of
1) carbon 2) carbon monoxide 3) hydrogen 4) None
31) The alloy of iron containing 15-20% Mn and 60% C is called
1) Steel 2) spiegeleisen 3) Pig iron 4) Stainless steel
32) Choose the incorrect statement related to the manufacture of steel.
1) The composition of steel can not be controlled during the bessemer converter process.
2) Iron ore, scrap iron and low grade pig iron can be used during bessemer converter process.
3) The composition of steel can be controlled during the open hearth process.
4) There is loss of iron during bessemer converter process due to the use of blast of air.

REFINING OF METALS
1) Impure tin can be refined by
1) Roasting 2) Liquation 3) Smelting 4) Calcination
2) The method which uses green wood poles to reduce the oxide impurites from impure metals is
called
1) Cupellation 2) Green wood process 3) Poling 4) Smelting
3) The metal which can be refined by distillation process is
1) Zn 2) Cd 3) Hg 4) All
4) The best method used to refine gold metal is
1) Distillation 2) Electrolysis 3) Bassemerization 4) Oxidation
5) The suitable method used to remove lead impurity from impure silver is
1) Poling 2) Cupellation 3) Distillation 4) All
6) Highly pure silicon can be obtained by
1) Electrolysis 2) Roasting 3) Zone refining 4) Liquation
7) The complex of nickel formed during Monds process is
1) NiCl4 2) Ni(CO)4 3) Ni(CO)6 4) K2[Ni (CN)4]
Note : Monds process is a vapour phase refining method of nickel. In this process, nickel is converted to volatile nickel
tetracarbonyl by heating in a stream of carbon monoxide at 330-350K. Then the complex is subjected to dissociation by
heating at higher temperature (450 - 470K) to get pure nickel
330-350K 450-470K
Ni + 4 CO Ni (CO) 4 Ni + 4CO
impure Volatile Pure

8) The vapour phase method used to purify zirconium is

1) Van Arkel method 2) Monds process 3) Gibbs method 4) Bayers process
Note : In the van Arkel method, Zirconium is heated in iodine vapour at about 870K to form volatile ZrI4. The latter
when heated over a tungsten filament at 2075K gives pure Zirconium.
870 K 2070K
Zr + 2I 2 Zr I 4
Zr + 2 I 2
impure (Volatile) Pure

Titanium can also be refined by this method.

JO JE VANCHEEL, THO THE LAHO

Periodic Table 1

PERIODIC TABLE

MENDELEEFS PERIODIC TABLE

Mendeleef proposed following periodic law and arranged elements in the increasing order of
atomic masses.
Mendeleefs Periodic law
"Physical and chemical properties of elements are periodic functions of their atomic
weights"
* The elements are arranged in horizontal rows and vertical columns.
* The horizontal rows are called periods. The number of elements in a period may vary. The first
three periods of the Mendeleef table are called as short periods. The other periods are known as long
periods.
* The vertical columns in the table are known as groups or families. The groups are sub divided
into two subgroups A and B. The elements arranged in a group possess similar properties.
* The long period of the Mendeleef periodic table consists of two rows of elements called as
series.
* He considered the similarities in the formulae and the properties of the compounds formed by
the elements.
* Mendeleef observed that elements with similar properties had
(i) Either almost the same atomic weights.
e.g. Fe(56), Co(59), Ni(59)
Os(191), Ir(193), Pt(195)
(ii) Or atomic weights which showed a constant increase
e.g. K(39), Rb(85), Cs(133)
Ca(40), Sr(88), Ba(137)
* The elements with low atomic weights are called typical elements. These are arranged in three
short periods of the periodic table.
* Group VIII of the Mendeleef table contains three triads, namely, (Fe, Co, Ni and Ru, Rh, Pd
and Os, Ir, Pt). These triads are called transition elements which include Sc(21) to Zn (30), lan-
thanides and actinides.
* From a study of adjacent elements and their compounds, Mendeleef was able to predict
the characteristics of certain elements which were found to be very accurate.
e.g.1) Eka Al - Gallium 2) Eka Si - Germanium 3) Eka B - Scandium

Comparison of properties predicted by Mendeleef with those observed.

S.No. Property As predicted by As observed

Mendeleeff experimentally
1 Name of the element Eka Aluminium Gallium
2 Atomic weight 68 70
-3
3 Density (g.cm ) 5.90 5.94
4 Formula of oxide (Eka Al)2 O3 Ga2O3
5 Formula of Chloride (Eka Al)Cl3 GaCl3

* He corrected the atomic weights of some elements like Beryllium, Indium, Uranium.
Periodic Table 2

Limitations :
* Zero group elements were not known at the time of Mendeleef.
* In every group lanthanides were placed though they have dissimilar properties.
* At some places it violates the increasing order of atomic weight rule.
Ar40 & K39
Co59 & Ni58
Te128 & I127
Th 232 & Pa 231
These four pairs are called anomalous pairs or inverted pairs.
* Elements with dissimilar properties were grouped together.
E.g. ' Th' is placed in III group and Ag is placed in I group.
* Atomic mass is taken as fundamental property.

MODERN LONG FORM OF PERIODIC TABLE

Modern periodic table was constructed by Neils Bohr based on modern periodic law.
Modern periodic law
The chemical and physical properties of elements are the periodic functions of their
atomic numbers and electronic configurations.
Above law was proposed by Moseley. He found the relation between atomic numbers (z) and the
frequencies ( ) of x- rays produced by them.
a z b

Where a & b are constants characteristic of elements

SALIENT FEATURES OF MODERN LONG FORM OF PERIODIC TABLE

Modern long form of periodic table consists of seven rows called periods and eighteen
columns called groups.

Groups:
* The 18 groups in the periodic table are numbered as IA , IIA, IIIB. .... VIII (3 groups) IB ,IIB,
IIIA - VIIA and zero group.
* I A to VII A group elements are called representative elements.
* Zero group elements are called inert gases.
* IB to VII B and VIII B group element are called transition elements.
* The elements present in a group show similar chemical properties as they have similar outer
electronic configuration.

Periods:
* Each period starts with alkali metals (IA) and ends with inert gas elements.
* The first period is a very short period with only two elements i.e., Hydrogen (H) & Helium (He).
* The second period starts with Lithium (Li) and ends with Neon (Ne) and contains 8 elements. It
is called first short period.
* The third period also contain 8 elements i.e., from Sodium (Na) to Argon (Ar). It is called
second short period.
* The fourth period is the first long period with 18 elements , it starts Potassium (K) &
ends with Krypton (Kr). It also includes 10 elements belonging to 3d series i.e., from
Scandium (Sc) to Zinc (Zn).
* The fifth period is the second long period with 18 elements, it starts with Rubidium (Rb) and
ends with Xenon (Xe). It also includes 10 elements belonging to 4d series i.e. from Yttrium (Y) to
Periodic Table 3
Cadmium (Cd).
* The sixth period is the longest period with 32 elements. It not only includes 10 elements belong-
ing to 5d series i.e., Lanthanum (La), Hafnium (Hf) to Mercury (Hg) but also contain 14 elements
belonging the 4f series called lanthanides (Cerium(Ce) to Lutetium (Lu)).
* The seventh is an incomplete period which starts with Fr. It includes the 14 elements belonging
to 5f series called actinides (Thorium (Th) to Lawrencium (Lr)).
* Lanthanides and actinides are placed below the period separately.

Advantages:
1. The chemical and physical properties of the elements can be studied easily.
2. Position of metals and nonmetals can be know.
3. The chemistry of transition elements can be studied along with d-block elements.

THE RELATION BETWEEN THE NUMBER OF ELECTRONS FILLED INTO THE SUB
SHELLS AND THE NUMBER OF ELEMENTS IN A PERIOD
In the long form of periodic table, there are seven periods according to the number of main shells
being filled up by electrons.
Each period starts with filling up of a new quantum level. In each period, the number of elements is
equal to the number of electrons filled into the subshells as shown below.

No. of Main and Total no of Total number of

the sub-energy levels electrons filled in elements in the
period {as (nl)} all the sub-levels period
1. 1s 2 2
2. 2s 2p 8 8
3. 3s 3p 8 8
4. 4s 3d 4p 18 18
5. 5s 4d 5p 18 18
6. 6s 4f 5d 6p 32 32
7. 7s 5f 6d -- incomplete

CLASSIFICATION INTO S, P, D & F BLOCKS

The elements in the periodic table are divided into s, p, d & f -blocks based on the type of sub -
shell into which the differentiating electron enters.
1) s - block
* The differentiating electron enters into s - orbitals of outer shell in s - block elements.
* The general outer electronic configuration is ns12
* These elements are present at the left hand side of the periodic table.
* IA group [Alkali metals] and IIA group [alkaline earth metals] elements belong to this block.
* These elements are strong metals and good reducing agents.
* The common oxidation states are +1 & +2 respectively for IA and IIA group elements.

2) p - block
* In p-block elements, the differentiating electrons enter into p-orbitals of outer shell.
* The general electronic configuration is ns 2 np1 6
* The IIIA to 'zero' group elements belong to this block. These are present at the right hand side
of the periodic table.
Periodic Table 4
Group III A Boron family ns2np1
Group IV A Carbon family ns2np2
Group V A Nitrogen family ns2np3
Group VI A Oxygen family ns2np4
Group VII A Halogen family ns2np5
Group O Inert gases ns2np6 (except He which has 1s2 configuration)
* These elements constitute nonmetals, metals and metalloids and inert gases.
* These elements can exhibit both negative and positive states.

3) d - block
* In d - block elements, the differentiating electron enters into d - orbitals of (n-1) shell.
* The general outer electronic configuration is (n-1)d1-10 ns1,2
* These elements are present in between s and p-block elements.
* Depending on the principal quantum number of d - orbital into which the last electron enters,
these elements are again divided into following series.
3d series Sc to Zn 4th Period
4d series Y to Cd 5th Period
5d series La, Hf to Hg 6th Period
6d series Ac - (incomplete) 7th Period
* All the d-block elements are metals and are usually called as transition elements.
* These elements show variable oxidation states, paramagnetism and color. They can effectively
form complex compounds, alloys and non-stoichiometric compounds.
* These elements and their compounds are good catalysts.
E.g., 1) Ni in hydrogenation of oils
2) Fe / Mo in Haber's process of synthesis of NH3.
3) Platinized asbestos in the manufacture of H2SO4.
* These elements can form alloys effectively.
E.g., Brass, Bronze, German silver, etc.,

4) f -block
* In f-block elements, the differentiating electrons enter into f-orbitals of (n-2) shell.
1-14 0 or 1 2
* The general outer electronic configuration is (n-2)f (n-1)d ns
* These elements belong to IIIB group and are placed below the table separately these are also
called as inner transition elements.
* The 14 elements from Cerium(Ce) to Lutetium (Lu) which follow the elements Lanthanum are
called as Lanthanoids or rare earth elements.
In these elements the differentiating electrons enter into 4f-orbitals and hence are also
called as 4f -series.
* The 14 elements from Thorium (Th) to Lawrencium (Lr), which follow Actinium are called
Actinoids. In these element the differentiating electrons enter into 5f-orbitals and hence these are also
known as 5f-series.
* All of these elements are radioactive. The elements after Uranium are called trans uranic ele-
ments. These are artificially prepared elements.
* These elements show +3 common oxidation state.
Periodic Table 5

s-block p-block
d-block

f-block

Classification based on chemical properties

The elements in the periodic table are classified into four groups based on their chemical proper-
ties and the electronic configuration.

1) Noble gas elements :

* The zero group elements are called noble or inert gases (He, Ne, Ar, Kr, Xe, Rn).
* The general outer electronic configuration is ns 2 np6 except for He (1s2).
* In these elements, all the shells are completely filled.
* Due to stable electronic configuration, these elements do not participate in bond formation.
* These elements exist as mono atomic gases.

2) Representative elements :
* The s & p-block elements except zero group elements are called representative elements.
* The outer electronic configuration is ns1-2 np 0 5
* In these elements, the outer shell is incompletely filled.
* This group includes metals, nonmetals and metalloids.
* These elements can share or gain or lose electrons to get octet configuration.

3) Transition elements :
* The d-block elements except II B group (Zn, Cd and Hg), are called as transition elements.
* In these elements the last two shells (n and n-1) are incompletely filled
* The general outer electronic configuration is (n-1)d1-10 ns1,2
* Due to small size, high nuclear charge and presence of incompletely filled d-orbitals, these
elements show characteristic properties as given below.
i) These elements are very hard and heavy metals with high melting and boiling points.
ii) These are good conductors of heat and electricity.
iii) They exhibit variable oxidation states.
E.g., Fe exhibits +2 and +3 oxidation states.
iv) The transition metal ions show colors due to d-d transitions.
v) They show paramagnetism due to presence of unpaired electrons.
vi) Transition metals and their compounds are good catalysts.
E.g., 1) Ni in hydrogenation of oils.
2) Fe / Mo in Haber's process of synthesis of NH3.
3) Platinized asbestos in the manufacture of H2SO4.
Periodic Table 6
vii) These elements can form alloys effectively.
E.g., Brass, Bronze, German silver, etc.,

4) Inner Transition elements :

* The f-block elements are called inner transition elements.
* In these elements the last three shells (n, n-1 and n-2) are incompletely filled.
* The general outer electronic configuration is (n-2)f 1-14 (n-1)d 0 or 1ns 2 .
* These elements belong to IIIB group and are placed below the table separately.
* The 14 elements from Cerium(Ce) to Lutetium (Lu) which follow the elements Lanthanum are
called as Lanthanoids or rare earth elements.
In these elements the differentiating electrons enter into 4 f-orbitals and hence are also
called as 4f -series.
* The 14 elements from Thorium (Th) to Lawrencium (Lr), which follow Actinium are called
Actinoids. In these elements the differentiating electrons enter into 5f-orbitals and hence these are also
known as 5f-series.
* All of these elements are radioactive. The elements after Uranium are called trans uranic ele-
ments. These are artificially prepared elements.
* These elements show +3 common oxidation state.

PERIODICITY
The recurrence of similar chemical and physical properties at regular interval of atomic numbers in
a periodic table is called Periodicity.
Periodic Properties : The properties which show periodicity.
E.g., (i) Density
(ii) Melting and boiling points
(iii) Hardness
(iv) Conductivity
(v) Magnetic property
(vi) Atomic radius
(vii) Ionic radius
(viii) Ionization potential
(ix) Electronegativity
(x) Electron affinity
(xi) Electropositivity
(xii) Valency
(xiii) Oxidation number
(xiv) Metallic and non metallic nature
(xv) Nature of oxides

ATOMIC RADIUS :
The average distance between the centre of the nucleus and the electron cloud of outermost orbit
is called atomic radius.
There are three types of atomic radii based on the nature of bonding.

(i) Crystal radius ( atomic radius ) : The half of inter nuclear distance between two adjacent atoms
in a metallic crystal.
It is applicable to metals.
e.g.
3.72
1) The distance between two Na atoms is 3.72 A0. Hence its crystal radius is =1.86 A o .
2
Periodic Table 7
5.24
2) The distance between two Cs atoms is 5.24 A0. Hence its crystal radius is =2.62 A o .
2

(ii) Covalent radius : The half of inter nuclear distance between two atoms held together by a
covalent bond.

0.99A 0

Bond length of Cl2

E.g., covalent radius of 'Cl' atom =
2
1.98
= = 0.99A 0
2
(iii) van der Waal's radius : The half of inter nuclear distance between two closest atoms of different
molecules attracted by van der Waal's forces.
Usually van der Wall's radii are 40% greater than crystal or covalent radii.
3.6
E.g., van der Wall's radius of Cl = = 1.86A 0
2

1.
86
A 0

Periodicity in atomic radius

In groups - Atomic radius increases down the group as the differentiating electron enters into the new
quantum shell. This outweighs the increase in nuclear charge.
E.g., The order of atomic radius in IA group is
Li < Na < K< Rb < Cs < Fr

In periods : Atomic radius decreases across the period from left to right as the nuclear charge and
atomic number increase. The differentiating electron enters into same shell.
In a given period IA group element is bigger in size and VII A group element is smaller in size. The
abnormal increase in case of zero group element is due to its van der Waal's radius.
E.g., Order of atomic size in 2nd period
Li > Be > B > C > N > O > F < Ne

In transition elements : The atomic size decreases slightly across the period in d-block elements
due to shielding effect of inner d- electrons.

In Lanthanoids : The atomic radius decreases with increase in atomic number in Lanthanoids due to
poor shielding effect of inner f - electrons. This is called Lanthanoid contraction.
Periodic Table 8
Consequences of Lanthanoid contraction
i) Lanthanoids possesses similar crystalline structures and hence their separation is difficult.
ii) Elements of 4d and 5d series show more similarity in their properties.
E.g., Zirconium (Zr), ( 4d series) and Hafnium (Hf), ( 5d series) have almost same atomic radii.

IONIC RADIUS
* The ionic radius decreases with increase in effective nuclear charge.
* In case of cations, the ionic radius decreases with increase in the positive charge.
A+ > A2+ > A3+ . .............
* In case of anions, the size increases with increase on the negative charge.
A- < A2- < A3- . .............
* In a group, for same type of ions the ionic radius increases from top to bottom.
E.g., The ionic radii of M+ ions in I A group elements increase in the following order.
Li+ < Na+ < K+ < Rb+ < Cs+ < Fr+
* In a given period, the ionic radius decreases with increase in effective nuclear charge for isoelec-
tronic ions.
C4- > N3- > O2- > F-
Nuclear charge 6 7 8 9
No. of electrons 10 10 10 10

IONIZATION ENERGY (I.E)

The minimum amount of energy required to remove an outer most electron from a gaseous neutral
atom in the ground state is called first ionization energy.
It is represented by I.E1.
A + I.E1
A+ + 1e-
neutral atom
The minimum amount of energy required to remove an outer most electron from a gaseous uni-
positive ion is called second ionization energy (I.E2).
A+ + I.E 2
A 2+ + 1e -
unipositive ion
Second ionization energy is always greater than the first as the effective nuclear charge increases
from A to A+.
In general I.E1 < I.E2 < I.E3 < I.E4 _ _ _ _ _

Factors affecting ionization energy

i) Atomic radius
Ionization energy decreases with increase in atomic radius as the nuclear attraction over outer
electron decreases.
1
Ionization energy
Atomic size
E.g., In IA group, ionization energies decreases with increase in atomic radius down the group.
Order ionization energy
Li > Na > K > Rb > Cs > Fr
2) Nuclear charge :
Ionization energy increases with increase in nuclear charge.
I.E nuclear charge
Periodic Table 9
3) Screening or shielding effect :
Reduction of nuclear attraction over the outer electrons due to presence of inner electrons is called
screening or shielding effect.
The order of shielding ability for different types of orbitals is given below.
s>p>d>f
Ionization energy decreases with increase in screening effect
1
I.E
Screening effect
4) Penetration power :
Ability to come closer towards nucleus is called penetration power. Greater the penetration power,
greater is the ionization energy.
I.E Penetraction power

Penetration power of different orbitals is given below.

s>p>d>f
5) Electronic Configuration
Atoms with ns2 np6 configuration or with half filled or completely filled sub shells are extra stable.
Hence their ionization energies are very high.
E.g. IIA group elements with ns2 (completely filled) and VA group elements with ns2 np3
(half filled) configurations possess higher ionization potentials.

Periodicity in ionization energy

In groups
Ionization energy decreases down the group as the atomic radius increases.
E.g. The order of ionization energy in IA group elements is Li > Na >K > Rb >Cs > Fr

In periods : In general, the ionization energy increases from left to right in a period with decrease in
atomic radius. But this increment is not regular.
In a given period, IIA (ns2) and VA (ns2np3) group elements have higher ionization energies than
elements in their next groups i.e., III A and VI A respectively. It is due to stable electronic configura-
tions.
E.g., The order of ionization energies in 2nd period is given below
Li < Be > B < C < N > O < F << Ne
2s2 2s22p3 2s22p6
2 2 3
'Be' with 2s (full filled) and 'N' with 2s 2p (half filled) configurations are more stable and hence
possess higher ionization potentials than 'B' and 'O' respectively.

Ne
F
Ionization Energy

2s22p3
N

C O
2s2
Be

B
Li

Atomic number(Z)
Periodic Table 10
In a given period alkali metals possess low ionization energies and inert gases possess very high
ionization energies.
Cs ---- Element with lowest ionization energy
He ---- Element with highest ionization energy.

In d-block elements : Due to shielding effect of inner d-electrons, the ionization energy is increased
slowly across the period in transition elements.

ELECTRON GAIN ENERGY (ELECTRON AFFINITY)

The amount of energy released when an electron is added to a neutral gaseous atom in the ground
state is called electron gain energy.
A 1e-
A -EA1
neutralatom
Addition of another electron to uni negative ion is difficult due to repulsions. Hence energy is
absorbed during the addition of second electron. Hence second electron affinity is positive.
A 1e -
A 2- +EA2
uninegative ion
Electron affinity values are not measured directly but can be indirectly determined from Born-
Haber cycle.

Factors effecting electron affinity :

* Electron affinity values are higher for smaller atoms with high effective nuclear charge.
* The elements with stable electronic configurations possess very low electron affinities.
* In the periodic table the element with highest electron affinity is Chlorine (Cl). The inert gases
have zero electron affinities.

Periodicity in electron affinity

In groups
In general, the electron affinity decreases with increase in size of the atom from top to bottom in a
group.
But due to small size, the first element possesses lower electron gain energy than the second
element in a given group.
E.g., In halogens, fluorine atom is smaller in size and hence the newly added electron experiences
repulsion from the electrons in the atom. Hence its electron affinity is less than that of chlorine (Cl)
In Periods
Generally electron affinities increase from left to right in a period with decrease in atomic size.
But this increment is not regular.
In a given period, the electron affinities of elements with stable electronic configurations are very
low.
E.g. The order of electron gain energies in 2nd period is given below
Li > Be> B< C>N<O<F>>Ne
Be (2s ) , N (2s 2p3) and Ne (2s22p6) have stable configurations and hence possess low
2 2

electron affinity values.

Periodic Table 11

O
C

Electron affinity
B N
Li 2s22p3

Be
2s2 Ne
Atomic number(Z)

ELECTRONEGATIVITY
The tendency of the atom of an element to attract the shared electron pair towards itself in a
hetero nuclear diatomic molecule is called Electronegativity.
Electronegativity values can be expressed by using following two scales.

1) Pauling scale :
In this scale, the electronegativity values of elements are calculated from the bond energies. The
difference in electronegativity of atom A & B in a molecule AB can be given as follows.
X A - X B 0.208 AB K .cal / mol
(or)
X A - X B 0.1017 AB K . J / mol
where X A Electronegativity of A
X B Electronegativity of B
AB polarity of bond A - B
AB E A-B E A-B
E A-B = Experimental bond energy of AB
E A-B = The bond energy of AB
E A-B E AA .E BB
On Pauling scale fluorine has highest electronegativity value of 4.0
Element Electronegativity
F 4.0
O 3.5
N 3.0
Cl 3.0
H 2.1
C 2.5

Mulliken Scale :
According to this scale, electronegativity is the average of ionization energy and electron affinity.
Periodic Table 12
Ionization energy + Electon affinity
Electronegativity =
2
In this scale, the electronegativity values are 2.8 times larger than those of pauling values. The
electronegativity values equal to those in pauling scale are obtained by using following formulae.

Electronegativity =
I.E in K J / mole + E.A in K.J / mol
544

Periodicity in electronegativity
Electronegativity decreases down the group as atomic size increases. Whereas it increases from
left to right in a period since the atomic size decreases.

Applications :
* The nature of bond formed between two atoms can be predicted from their electronegativity
difference.
If the electronegativity difference is 1.7, the bond would be more than 50% ionic.
If the electronegativity difference is less than 1.7, the bond formed will be more than 50% cova-
lent.
* From the electronegativity values, proper chemical formulae of compounds can be written.
* It is possible to calculate oxidation states by comparing electronegativity values.

VALENCY
Valency indicates the combing power of an atom. It is equal to the number of hydrogen atoms or
double the number of oxygen atoms with which the atom of an element combines.
The valency with respect to hydrogen is equal to group number in IA to IVA groups. But in VA to
Zero group, valency with respect to hydrogen is equal to (8 - group number).

valency with respect to hydrogen.

IA IIA IIIA IVA VA VIA VIIA O
Valency 1 2 3 4 3 2 1 O
Hydride LiH BeH2 B2H6 CH4 NH3 H2O HF -

The maximum valency with respect to oxygen or fluorine is equal to the group number

Valency with respect to oxygen or fluorine

IA IIA IIIA IVA VA VIA VIIA O
Valency 1 2 3 4 5 6 7 O
Oxide Na 2 O MgO Al2O3 CO 2 P2 O 5 SO 3 Cl2O 7 -
Fluoride NaF MgF2 AlF3 CF4 PF5 SF6 IF7 -

* An element can show more than one valency (multiple valency)

OXIDATION STATES (OR) OXIDATION NUMBERS

The formal charge acquired by an atom in a given species is called oxidation state or oxidation
number
Periodicity
The elements in a given group exhibit mostly one oxidation number.
Periodic Table 13
* The maximum positive oxidation state shown by IA to VIIA group elements is equal to the group
number.
E.g.,

IA IIA IIIA IVA VA VIA VIIA Maximum

positive
oxidation
number +1 +2 +3 +4 +5 +6 +7

* The elements of groups from IVA to VIIA also exhibit negative oxidation states equal to group
number -8.
E.g.,
IVA VA VIA VIIA
Oxidation number -4 -3 -2 -1
* The p-block elements can show variable oxidation states-both negative and positive.
E.g., Phosphorus can show +3 (PCl3) and +5 (PCl5) oxidation states.
Inert pair effect : The reluctance of the electron pair in the outer 'ns' orbital to get unpaired and
involved in the bond formation is called inert pair effect.
Inert pair effect is caused due to poor shielding effect of inner f-electrons.
Due to inert pair effect, the heavier elements of IIIA, IVA and VA group elements are more stable
in oxidation numbers less by two units of the group oxidation number.
E.g., (i) Thallium (Tl) is more stable in +1 oxidation state then in +3 state.
(ii) Tin (Sn) and Lead (Pb) are more stable in +2 oxidation state than in +4 oxidation state.
(iii) Bismuth (Bi) is more stable in +3 state than in +5 state.

* d-block elements show variable oxidation numbers. Their common oxidation state is +2 due to
presence of two electrons in the ns orbital.
* Ruthenium (Ru) and Osmium (Os) can show a maximum oxidation state of +8.
* Lanthanoids show +3 as common oxidation state.

ELECTROPOSITIVITY
The tendency of an element to lose electrons is called electropositivity.
Electropositivity increases with increase in the atomic size. It increases down the group and de-
creases across the period from left to right. Highly electropositive elements are called metals. They
possess low ionization energies.
IA and IIA group elements are highly electropositive elements.

Metallic and Non metallic nature:

* The elements with low electronegativity (high electropositivity) are called metals.
* The elements with high electronegativity are called non metals.
Periodicity
* In a given group metallic nature increases from top to bottom with decrease in electronegativity.
* In a given period non metallic nature increases from left to right with increase in electronegativity.
Periodic Table 14
* In a given period IA and IIA group elements are stronger metals whereas halogens are stronger
non metals.

NATURE OF OXIDES
* Oxides are the binary compounds of elements with oxygen. These are of three types as follows.
i) Basic oxides : These oxides dissolve in water by giving alkaline solutions.
E.g., Na2O, CaO etc.......
Na 2 O + H 2 O
2 NaOH
Ca OH 2
CaO + H 2O
Metal oxides are usually basic in nature
ii) Acidic oxides : These oxides dissolve in water by giving acidic solutions.
E.g., CO2 , SO3 , Cl2O7 etc.,
CO 2 + H 2 O
H 2 CO 3
Cl 2 O 7 + H 2 O
2HClO 4
SO 3 + H 2 O
H 2SO 4
Non metal oxides are usually acidic in nature.
iii) Amphoteric oxides: These oxides show both acidic and basic properties.
E.g., BeO, Al2O3 etc....

Periodicity in nature of oxides

In a group, the basic nature of oxides increases down the group.
E.g., The increasing order of basic nature in oxides of IA group elements is
Li2O < Na2O < K2O < Rb2O < Cs2O
In a period, the acidic nature of oxides increases from left to right.
E.g., In third period, the nature of oxides vary as follows.

Group IA IIA IIIA IVA VA VIA VIIA

Oxides Na2O MgO Al2O3 SiO2 P4O10 SO3 Cl2O7
Very Very
Strong Weak Weak Strong
Nature Amphoteric weak strong
Base Base acid acidic
acid acid

DIAGONAL RELATIONSHIP
In the periodic table, an element of second period in a group is similar in properties with the third
period element of next group. This is known as diagonal relationship.
E.g., Following diagonally placed elements exhibit similar chemical properties.

Group IA IIA IIIA IVA

2nd period Li Be B C

3rd period Na Mg Al Si

Diagonally related elements possess similar ionic sizes, similar electronegativities and same polar-
izing power.
Periodic Table 15
ionic charge
Polarizing power =
( ionic radius )2
E.g., Be and Al exhibit similar properties as given below.
* BeO and Al2O3 amphoteric oxides.
* Carbides of both the elements produce methane (CH4) gas on hydrolysis.
Al4C3 + 12H2O 4Al(OH)3 + 3CH4
Be2C + 4H2O
2 Be(OH)2 + CH4
 SOLID STATE CHEMISTRY
IIT-JEE
TYPES OF CRYSTALS
1) The characteristics of crystalline solids
1) Definite shape 2) Long range orders 3) Anisotropic 4) All
2) Choose the incorrect statement
1) Amorphous solids are isotropic and have only short range orders.
2) Crystalline solids have sharp melting points.
3) Amorphous solids have sharp melting points.
4) Amorphous solids are also called as super cooled liquids.
3) Match the following.
A) Ionic crystals 1) Diamond, Silicon etc.,
B) Molecular crystals 2) Cu, Zn, Na etc.,
C) Covalent crystals 3) Solid CO2, I2 etc.,
D) Metallic crystals 4) KCl, Na2SO4 etc.,
The correct match is
A B C D
1) 1 2 4 3
2) 4 3 2 1
3) 4 3 1 2
4) 3 4 1 2
4) The substance which exhibits electrical conductivity in the solid state is
1) NaCl 2) Diamond 3) Silver 4) Both 1 & 3
5) The molecular crystal which shows electrical conductivity is
1) Diamond 2) Silica 3) Silver 4) Graphite
6) Conversion of amorphous substances into crystalline state by slow cooling of liquids of
amorphous substances is called
1) Crystallization 2) Annealing 3) Racemization 4) None
7) Low melting points, bad electrical conductivity and softness are the characteristics of
1) Ionic crystals 2) Covalent crystals 3) Metallic crystals 4) Molecular crystals
8) The type of attractions present between molecules in ice are
1) vander Waals attractions 2) Covalent bonds
3) Hydrogen bonds 4) Both vander Waals attractions and Hydrogen bonds
9) Ionic solids are generally
1) Good conductors of electricity 2) Quite hard 3) Quite brittle 4) Volatile

CRYSTAL SYSTEMS
1) The number of basic crystal systems based on their symmetry elements and crystallographic
parameters is
1) 14 2) 7 3) 230 4) 32
Note : In the seven basic or primitive crystal systems, the lattice points are present only at the corners of unit cell.
But in case of fourteen Bravais lattices, the lattice points are also present at the centre or at the edges or at the centre of
faces of unit cell.
2) Match the following
Crystal system Parallelopiped dimensions
A) Cubic 1) a b c; 900
B) Tetragonal 2) a = b = c; 900
C) Orthorhombic 3) a = b c; 900
D) Triclinic 4) a b c; 900
 Correct Matching is
A B C D
1) 2 3 1 4
2) 2 3 4 1
3) 2 4 3 1
4) 4 2 1 3
3) Which of the following crystal system has not been correctly characterized ?
1) Rhombohedral ; a = b = c ; 900
2) Monoclinic ; a b c ; 900 ; 900
3) Hexagonal ; a = b c ; = =900 , 1200
4) Orthorhombic ; a = b = c;
4) Match the following
A) Triclinic 1) NaCl, diamond & ZnS
B) Cubic 2) KNO3, - S & MgSO4.7H2O
C) Orthorhombic 3) CuSO4. 5H2O, K2Cr2O7 & H3BO3
D) Monoclinic 4) -S, NaHCO3 & FeSO4.7H2O
Correct matching is
A B C D
1) 3 1 4 2
2) 2 3 4 1
3) 1 2 3 4
4) 4 3 2 1
5) Rhombohedral crystal system is present in
1) KMnO4 2) Calcite 3) Bi 4) Calcite
Note: Other examples are KMnO 4,Bi, As, Sb, NaNO 3 etc.,
6) Choose the incorrect statement (s)
1) Ice and quartz can crystallise in either hexagonal or trigonal forms
2) Cinnabar has hexagonal crystal system
3) Tetragonal crystal system is present in CaF2
4) 1 & 2 only.
7) The substance with monoclinic crystal system is
1) Glaubers salt 2) - sulfur 3) K2Cr2O7 4) All
Note: - sulfur, Monoclinic gypsum, NaHCO 3, FeSO 4.7H 2O etc.,
8,) The parameters of crystal system in graphite are
1) a = b c ; 900 ; 1200 2) a = b = c ;
3) a b c ; 4) All
Note : Other examples with hexagonal arrangement are Mg, SiO 2 and ZnO
9) The crystal system present in white tin is
1) Hexagonal 2) Tetragonal 3) Triclinic 4) Cubic
Note : Other examples with tetragonal arrangement are TiO 2 , NiSO 4 , SnO 2 and K4 [Fe(CN) 6 ]
10) The crystal system without any rotational axis of symmetry is
1) Triclinic 2) Cubic 3) Hexagonal 4) None
11) The relation between crystallographic angles in monoclinic crystal system is
1) 900 ; 900 2) 900
3) 4) 900 ; 1200
12) The correct parallelopiped dimensions for the crystal system in baryta (BaSO4) are
1) a b c; 900 2) a b c; 900
3) a b c; 900 4) a b c;
13) The crystal system with the crystallographic angles 900 is
1) Cubic 2) Tetragonal 3) Orthorhombic 4) All
14) The relation between crystallographic axes in Na2B4O7.10H2O and H3BO3 is
1) a b c 2) a = b = c 3) a b = c 4) a = b c
Hint : Na2B 4O 7.10H 2O - Monoclinic
H 3BO 3 - Triclinic
15) The changes in the crystallographic parameters in the following conversion are
S S
1) a b c a = b = c 2) 900 ; 900
3) 4) a b c a b c
16) The unit cell present in the crystal lattice of diamond is
1) Cubic 2) Tetragonal 3) Hexagonal 4) Trigonal
17) CuSO4.5H2O belongs to
1) Triclinic system 2) Cubic system 3) Tetragonal system 4) Hexagonal system
18) The number of bravais lattices possible in a cubic crystal system is equal to
1) 1 2) 2 3) 3 4) 4
Note : Simple cube (P), fcc (F) and bcc ( I ) are possible for cubic system.
19) In which of the following bravais systems, only the primitive arrangement of lattice points in the unit
cell is possible ?
1) Hexagonal 2) Trigonal 3) Triclinic 4) All
Note : In the primitive unit cell, the lattice points are present only at the corners.
20) The types of bravais lattices possible for orthorhombic system are
1) P only 2) P & I 3) P, I & F 4) P, I, F & C
Note : P - Primitive
I - Body - centred
F - Face - centred
C - End - centred
21) The number of C3 axes (three fold axes) of symmetry present in a cubic system
1) 2 2) 3 3) 4 4) No C3 axis of symmetry
Note : C 3 axis of symmetry passes through the diagonally opposite corners
22) Which of the following crystal system possesses C6 axis of symmetry ?
1) Trigonal 2) Hexagonal 3) Cubic 4) All

PACKING OF ATOMS & TYPES OF UNIT CELLS

1) The type of unit cell obtained when two dimensional square close packed layers are arranged over
each other such that the spheres in the second layer are present exactly over the spheres of first
layer is
1) Body centred cubic 2) Primitive cubic 3) Face centred cubic 4) Hexagonal
2) The two dimensional square close packed layers are arragenged such that the spheres in evey next
layer are arraged over the voids of the first layer. The unit cell obtained is
1) BCC 2) FCC 3) HCP 4) CCP

3) The unit cell present in ABAB.... type of closest packing of atoms is

1) Tetragonal 2) Hexagonal 3) Face centred cube 4) Primitive cube
Note : There are two types of closest packing layers in three dimensional hexagonal close packing arrangement. The spheres in
the second layer (B) are present over the voids of one type in first layer (A)

4) The unit cell present in ABCABC... type of closest packing of atoms is

1) Hexagonal 2) Primitive cube 3) Body centred cube 4) Face centred cube
Note : In the face centred cube or cubic close packing, the closest packing layers are arranged in ABCABC pattern.
The spheres in the second layer (B) are arranged over one type of voids in the first layer (A). whereas the spheres in the third
layer (C) are placed over the second type of voids of first layer (A)
5) The co-ordination number in body centred cubic lattice is
1) 6 2) 8 3) 12 4) 4

6) The number of nearest atoms surrounding a given atom in a metallic crystal containing primitive
cubic unit cell is
1) 6 2) 8 3) 12 4) 4

7) The co-ordination number in hcp and ccp type of metallic crystals is

1) 4 2) 8 3) 12 4) 6

8) The number of atoms per a single primitive cubic unit cell is

1) 8 2) 4 3) 2 4) 1
 Note : The atom at the corner is shared amongst eight unit cell
1
no. of atoms per unit cell = 8 x 8 =1

9) The number of atoms per a single body centred unit cell is

1) 1 2) 2 3) 4 4) 9

Hint : There is one atom at the centre of the unit cell along with atoms at eight corners
1
no. of atoms per unit cell = 1+ (8 x 8 ) =2

10) The number of atoms per a single face centred cubic unit cell is
1) 2 2) 4 3) 8 4) 12

Hint : In the face cented cubic unit cell, there are atoms at of 6 faces along with atoms at 8 corners.
1 1
no. of atoms = (8 x 8 ) + (6 x 2 ) = 4

11) The number of atoms in an end centred cubic unit cell is

1) 2 2) 1 3) 4 4) 8
Hint : In the end centred cubic unit cell, there are two atoms at the centres of two opposite faces along with atoms at eight
corners.
1 1
no. of atoms = (8 x 8 ) + (2x 2 ) = 2

12) The number of atoms in hexagonal prismatic unit cell is

1) 2 2) 4 3) 6 4) 12

1 1
Note : contribution from top & bottom layers 2x[(6x 6 ) 2 ] 3
contribution from middle layer = 3
Total no.of atoms = 3 + 3 = 6
13) The relation between radius (r) of atom and edge length (a) in the primitive cubic unit cell of
closest packed atoms is
1) r = 2a 2) r = a / 2 3) r = a 4) r = 4a
14) The relation between radius (r) of atom and edge length (a) in the body centred cubic unit cell of
closest packed atoms is
3 2 3
1) r = a 2) r = a 3) r = 2a 4) r = a
4 4 2

Derivation :
In BCD
2 2 2 2 2 2
BC BD DC a a 2 a
In ABC
2 2 2 2 2 2 2 2
AC AB BC a BC a 2a 3a
But AC 4 r
AC 4 r 3a
3
r a
4

15) The relation between radius (r) of atom and edge length (a) in the face centred cubic unit cell is
3 2 3
1) r = a 2) r = a 3) r = 2a 4) r = a
4 4 2

Derivation :
In ABC
2 2 2
AC AB BC
2 2 2 2
4r a a 2a
4r 2a
2
r a
4

16) The metal which crystallises in simple cubic arrangement is

1) Po 2) Al 3) Mg 4) All
17) The type of unit cell present in sodium metal is
1) BCC 2) FCC 3) HCP 4) none
Note : Other examples with bcc structure are K, Rb, Cs, Ba, Cr, Mo and W
18) The metal which has fcc arrangement in its crystal is
1) Cs 2) Al 3) Zn 4) W
Note : Other examples with fcc arrangement are Cu, Au, Pb, Pt, Pd, Ni and Ca
19) The metal which has hcp arrangement
1) Be 2) Mg 3) Zn 4) All
Note : Other examples are Cd, Co, Ti & Tl
20) All the noble gases, except helium, crystallise in
1) hcp structure 2) ccp structure 3) bcc structure 4) rhombic structure
Note : Helium crystallises in hcp structure
21) The crystal structure in solid H2 is
1) hcp 2) ccp 3) bcc 4) All
22) If the atomic radius of Cs is 235 pm, then the edge length of unit cell in Cs metal will be
1) 54.27 pm 2) 542.7.A 0 3) 54.27 X 10-10m 4) 5.427.A0
Note : 1 Picometer (pm) = 10 -12 . meters
= 10-2A0
23) The edge length of unit cell in Cu metal is 3.62 A0. The atomic radius of Cu will be
1) 1.28 A0 2) 3.62 A0 3) 1.81 A0 4) 1.52 A0
Note : Cu crystallises in fcc structure
24) The length of a face diagonal of a simple cubic unit cell is 120 pm. The radius of the atom is
1) 60 pm 2) 42.4 pm 3) 72 pm 4) 47.3 pm
25) The edge length of unit cell in potassium metal, which crystallises in body centred cubic lattice, isy
cm. The length of body diagonal of the unit cell is
3
1) 2 y cm 2) 3 y cm 3) y cm 4) 4 2 y cm
4
Hint : There are three atoms touching each other along the body diagonal of the body centred cubic unit cell.
Length of body digonal = 4r = 3 a.
26) Chromium is crystallised in body centred cubic structure. The edge length of unit cell in chromium
is 293.3 pm. The distance between two nearest atoms in the unit cell is
1) 63 pm 2) 293.3 pm 3) 127 pm 4) 254 pm
Hint : The two nearest atoms in bcc are present along the body diagonal.

3
Nearest distance = d = 2r = a
2
27) The nearest distance (d) between two atoms in Nickel metal is 248 pm. The edge length (a) of the
unit cell will be
1) 124 pm 2) 350.6 pm 3) 68 pm 4) 412 pm
Hint : The two nearest atoms in fcc are arranged along the face diagonal of the unit cell.

3
Nearest distance (d) = 2r = a ( 4r = 2 a)
2
Note: Nickel crystallises in face centred cubic lattice.
28) A metal crystallises into a lattice containing a sequence of layers of ABC ABC-----. If the radius of
metal atoms is 174 pm, then the distance between the two successive layers (i.e., A and B) is
1) 348 pm 2) 174 pm 3) 284. 2 pm 4) 492. 2 pm
Hint : ABCABC ---- pattern gives rise to face centred cubic lattice. The layers (ABCA) are present perpendicular to the body
diagonal of the unit cell.
length of body diagonal
The distance between two successive layers = 3

3a 3 4 2
= = . r 2r
3 3 2 3

29) Magnesium crystallises into a lattice containing closely packed layers in ABAB____ pattern. The
distance between each successive layers is 217 pm. What is the radius of magnesium atom?
1) 133 pm 2) 217 pm 3) 108.5 pm 4) 266 pm
Hint: ABAB---- pattern of arrangement of layers is otherwise known as hexagonal cubib packing. The distance between two
successive layers in this type of packing is same as that of cubic close packing i.e.,
 2
2r
3

30) The volume occupied by atoms in a primitive cubic unit cell is (where a is edge length)
3 3 3
4 a 4 3 4 2 4 3
1) 2) 2 x a 3) 4 x a 4) r
3 2 3 4 3 4 3
31) The volume occupied by atoms in a body centred cubic unit cell is (where a is edge length)
3 3 3
4 a 4 3 4 2 4 3
1) 2) 2 x a 3) 4 x a 4) r
3 2 3 4 3 4 3
32) The volume occupied by atoms in a face centred cubic unit cell is (where a is edge length)
3 3 3
4 a 4 3 4 2 4 3
1) 2) 2 x a 3) 4 x a 4) r
3 2 3 4 3 4 3
33) The percentage of packing of a simple cubic unit cell is
1) 52.4% 2) 47.6% 3) 74% 4) 68%
The volume occupied by the atoms in a single unit cell
Hint: The packing fraction of a unit cell =
The volume of the unit cell

4 3 4 a 3
r
3 3 2
The packing fraction of body centred cubic unit cell = = = 0.5238
a 3 a 3 6

The percentage of packing = 0.5238 X 100 52.38%

34) The percentage of void volume in a simple cubic unit cell is

1) 47.6% 2) 68% 3) 52.4% 4) 20%
35) The percentage of packing of a body centred cubic unit cell is
1) 74% 2) 68% 3) 52.4% 4) 47.6%
3
4 3 4 3
2 X r 2 X a
3 3 4 3
Hint: The packing fraction of body centred cubic unit cell = = = 0.68
a 3 a 3 8

The percentage of packing = 0.68 X 100 68%

36) The percentage of packing of hcp and ccp type of unit cells is
1) 74% 2) 52.4% 3) 92% 4) none
3
4 3 4 2
4 X r 4 X a
3 3 4 2
Hint: The packing fraction of cubic close packed unit cell = = = 0.74
a 3 a3 6

The percentage of packing = 0.74 X 100 74%

Note: The packing fraction of hexagonal cubic packed unit cell is also 0.74

37) The percentage of void volume in face centred cubic lattice is

1) 26% 2) 0% 3) 32% 4) 12%
38) The atomic radius of aluminium is 1.26A 0. The density of it in the solid state is
1) 3.33 g.cm-2 2) 3.7g.cm-3 3) 2.31g.cm-3 4) 3.96g.cm-3
Formula :
M 1
density ( ) = Z. N . 3
a
 where Z = number of atoms in a unit cell
M = Molar mass
N = Avogadro number
a3 = Volume of the unit cell
a = edge length
Note : Aluminium crystallises in fcc structure.
39) The cubic unit cell of a metal ( molar mass 63.55g.mol-1) has an edge length of 362 pm. Its density
is 8.92 g.cm-3. The type of unit cell is
1) primitive 2) face centred 3) body centred 4) end centred
40) A metal has a density of 1.984 g.cm-3 and it crystallises in face centred cubic crystal with edge
length equal to 630 pm. The molar mass of the metal is
1) 37.35 g.mol-1 2) 56.02 g.mol-1 3) 74.70 g.mol-1 4) 65.36 g.mol-1
41) The numbers of tetrahedral and octahedral voids respectively present in closest packed crystals
containing X number of spheres are
1) 2X and X 2) X and 2X 3) 4X and 2X 4) 4X and X
Note: The number of trigonal voids is equal to 8X.
42) The ratio of radius of trigonal void to the radius of the spheres in closest packed arrangement is
1) 0.414 2) 0.155 3) 0.225 4) 0.732

Derivation:
BE
In BDE, cosDBE =
BD
o
rsphere
cos30 =
rsphere rvoid
rsphere rsphere
rsphere rvoid o
2.
cos30 3
rvoid =1.155 rsphere rsphere 0.155 rsphere
rvoid
0.155 rsphere
rsphere

43) The ratio of radius of tetrahedral void to the radius of the sphere in closest packed arrangement is
1) 0.414 2) 0.225 3) 0.732 4) None

Derivation:
AC
In OAC , sinAOC =
AO
o ,
109 28 rsphere
sin = ( AOB 109o 28, )
2 rsphere rvoid

rsphere rsphere
rsphere rvoid o ,

sin 54 44 0.8164
rvoid =1.225 rsphere rsphere 0.225 rsphere
rvoid
0.225 rsphere
rsphere

44) The ratio of radius of octahedral void to the radius of the spheres in closest packed arrangement is
1) 0.414 2) 0.155 3) 0.225 4) 0.732
 Derivation:
BD
In ABD , cosABD =
AB
o
rsphere
cos45 =
rsphere rvoid

rsphere
rsphere rvoid o
2 rsphere
cos45
rvoid =1.414 rsphere rsphere 0.414 rsphere
rvoid
0.414 rsphere
rsphere

45) The ratio of radius of cubic void to the radius of surrounding closely packed atoms whose centres
lie at the corners of a cube is
1) 0.414 2) 0.155 3) 0.225 4) 0.732

IONIC CRYSTALS
1) In the following diagram, the circles filled with black color represent the cations, whereas the big
circles represent the anions.

which of the following is the correct statement relating to above diagrams

1) The cation in diagram A is unstable.
2) The cation in diagram B is stable.
3) The cations in both the diagrams A & B are stable.
4) All
Note: The state of the atom or ion occupying any void in a crystal lattice is stable only when it is touching the surrounding
atoms or ions.
2) Match the following
Limiting radius ratio Geometry
A) 0.155 - 0.225 1) Tetrahedral
B) 0.225 - 0.414 2) Octahedral
C) 0.414 - 0.732 3) Trigonal
D) 0.732-0.999 4) Body centred cubic
The correct matching is
A B C D
1) 1 3 2 4
2) 3 2 4 1
3) 3 1 2 4
4) 1 2 4 3
3) Match the following
Co-ordination number Limiting radius ratio
A)3 1) 0.155-0.225
B) 4 2) 0.225-0.414
C) 8 3) 0.414-0.732
D) 6 4) 0.732-0.999
Correct matching is
A B C D
1) 1 2 3 4
2) 1 2 4 3
3) 1 3 2 4
4) 2 3 4 1
4) The limiting radius ratio for an ionic compound AB is 0.427. The smaller cation A+ will be more
stable when it occupies
1) Tetrahedral voids 2) Octahedral voids 3) Trigonal voids 4) Body centred cubic voids
Note: The cation can touch the anions when it occupies trigonl or tetrahedral voids, but it will be more stable in octahedral
void as it is surrounded by more number of anions. It will be less stable in body centred cubic void, even though it is
surrounded by even more anions, as it cannot touch the anions
5) The Cl- ions are arranged in expanded cubic close packing in NaCl crystal. The radii of Na+ and
Cl- ions are 95pm and 181 pm respectively. The type of voids occupied by Na+ ions is
1) Octahedral 2) Tetrahedral 3) Trigonal 4) All
r
Na
Hint: r 0.5248
Cl

6) The crystal structure present in NaCl is called

1) Fluorite structure 2) Rock-salt structure 3) Anti-fluorite structure 4) Spinel structure
Note : In Rock-salt structure, the bigger anions occupy the lattice points of expanded face centred cubic lattice. The smaller
cations occupy all the octahedral holes. The limiting radius ratio is in between 0.414 and 0.732. The co-ordination numbers
cation and anion are (6:6). The general formula of ionic compounds having this structure is AB.
Examples : NaCl, KCl, MgO, CaO, SrO etc.,

7) The number of NaCl units present in a single unit cell of NaCl crystal is
1) 1 2) 2 3) 4 4) 6
+
8) The number of octahedral holes occupied by Na ions in a single unit cell of NaCl is
1) 4 2) 8 3) 2 4) Zero
9) Which of the following does not crystallise in the rock salt structure
1) NaCl 2) KCl 3) CsCl 4) MgO
Note : Usually halides of Cesium assume BCC structures as the limiting radius ratio is greater than 0.732
10) The number of nearest Cl- ions around an Na+ ion in NaCl crystal is
1) 8 2) 6 3) 4 4) 12
- -
11) The number of nearest Cl ions arround a Cl ion in NaCl crystal is
1) 8 2) 6 3) 4 4) 12
12) The radii of Na+ and Cl- ions are 95 pm and 181 pm respectively. The edge length of unit cell in
NaCl is
1) 457 pm 2) 552 pm 3) 190 pm 4) 362 pm
Note : edge length in NaCl = 2rc+ 2ra
13) The crystal structure present in CsCl is referred to as
1) FCC 2) BCC 3) HCP 4) None
Note : BCC structure is present when the limiting radius ratio isgreater than 0.732. The anions occupy the lattice points of
simple cubic lattice. The cations occcupy centred cubic voids. This structure can be considered as interpenetrating primitive
cubic lattices of cation and anion.
The co-ordination numbers are (8:8). The number of formula units present per a single unit cell is one (one cation and
one anion). The general formula is AB.
Examples : CsCl, CsBr, CsI, CsCN, TlCl, TlBr, TlI, TlCN etc.,

14) The number of nearest Cl- ions present around a Cs+ ions in CsCl crystal is
1) 6 2) 8 3) 12 4) 4
+ +
15) The number of nearest Cs ions present around a Cs ion in CsCl crystal is
1) 8 2) 6 3) 4 4) 12
Hint : If only Cs+ ions are considered they occupy lattice points of primitive cubic lattice
16) The number of second nearest Cs+ ions present around a Cs+ ion in CsCl is
1) 4 2) 8 3) 12 4) 6
17) The radii of Cs+ and Cl- ions are 1.69 and 1.81 respectively. The edge length of the unit cell in
CsCl will be
1) 7 2) 3.38 3) 4.04 4) 3.5
Hint : In BCC, the ions touch along the body diagonal
Length of body diagonal = 2rc+2ra = 3a
18) The ionic compound which crystallises in anti-fluorite structure is
1) NaCl 2) Na2O 3) CaF2 4) Al2O3
Note : In the anti-fluorite structure, anions are arranged in cubic closest packing and cations occupy all the tetrahedral
voids. There are four anions and eight cations per unit cell of this structure and hence, the general formula of an ionic
compound is A8B4 or A2B.
The ideal radius ratio is between 0.225 - 0.414. But this ratio is not always maintained.The co-ordination numbers of
cation and anion are (4:8).
Examples : Na2O, K2O, Li2O, Rb2O, K2S, Cl2O, Na2S etc.,

19) In a unit cell of an ionic crystal, anions (Y) occupy the lattice points of face centred cubic lattice
and cations (X) occupy all the tetrahedral voids. The formula of the ionic compound will be
1) XY2 2) X2Y2 3) X2Y 4) XY
20) The number of anions per a single unit cell in antifluorite structure is
1) 2 2) 4 3) 8 4) 1
21) The type of voids occupied by cations in antifluorite structure is
1) Octahedral 2) Tetrahedral 3) Trigonal 4) Body centred cubic
22) The co-ordination number of Na+ ions in Na2O is
1) 2 2) 4 3) 8 4) None
23) The type of voids occupied by O2- ions in Na2O crystal is
1) Tetrahedral 2) Octahedral 3) Body centred cubic 4) Trigonal
24) The number of Na+ ions present per a single unit cell in Na2O crystal is
1) 4 2) 2 3) 8 4) 12
25) The fluorite crystal structure is present in
1) NaF 2) CaF2 3) AlF3 4) CsF
Note : In the fluroite structure, the cations are arranged into cubic close packing and the anions occupy all the tetrahedral
voids. Thus there are four cations and eight anions per a unit cell. Hence the formula of ionic compound is A4B8 or AB2.
The co-ordination numbers of cation and anion are (8:4).
Examples : CaF2, ZrO2, UO2, ThO2, BaF2, BaCl2, SrCl2, PbCl2 etc.,

26) The number of anions per a single unit cell in fluorite structure is
1) 2 2) 4 3) 8 4) 1
27) The type of voids occupied by anions in fluorite structure is
1) Octahedral 2) Tetrahedral 3) Trigonal 4) Body centred cubic
2+
28) The co-ordination number of Ca ions in CaF2 is
1) 2 2) 4 3) 8 4) None
2+
29) The type of voids occupied by Ca ions in CaF2 crystal is
1) Tetrahedral 2) Octahedral 3) Body centred cubic 4) Trigonal
30) The number of Ca2+ ions present per a single unit cell in CaF2 crystal is
1) 4 2) 2 3) 8 4) 12
2+ -
31) The radii of Ca and F ions respectively are 100 pm and 131 pm. The edge length of the unit cell
in CaF2 is
1) 231 pm 2) 533.5 pm 3) 462 pm 4) 362.5 pm
Hint: The Fluoride ions are present along the body diagonal at one fourth distance from the corner of the cube. Hence the
distance between calcium and fluoride ions is 1/4th of length of body diagonal.
32) The substance containing zinc-blende crystal structure is
1) NaCl 2) ZnCl2 3) BeO 4) CsCl
Note: In zinc-blende or sphalerite structure, anions occupy the face centred cubic lattice points and cations occupy half of
the tetrahedral holes (of one type). The ideal radius ratio is in between 0.225 to 0.414. There are four anions and four
cations in the unit cell. Therefore the formula is A4B4 or AB. The co-ordination numbers of cation and anion are (4:4).
Examples: ZnS, BeO etc.,
33) The number of anions per a single unit cell in zinc-blende structure is
1) 2 2) 4 3) 8 4) 1
34) The type of voids occupied by cations in zinc-blende structure is
1) Octahedral 2) Tetrahedral 3) Trigonal 4) Body centred cubic
35) The co-ordination number of Zn2+ ions in ZnS is
1) 2 2) 4 3) 8 4) None
2-
36) The type of voids occupied by S ions in ZnS crystal is
1) Tetrahedral 2) Octahedral 3) Body centred cubic 4) Trigonal
2+
37) The number of Zn ions present per a single unit cell in ZnS crystal is
1) 4 2) 2 3) 8 4) 12
2-
38) The co-ordination number of S ions in ZnS is
1) 2 2) 4 3) 8 4) None
39) The compound containing spinel structure is
1) MgAl2O4 2) Fe2O3 3) ThO2 4) KCl
Note: In spinel structure, the oxide ions are arranged in cubical closest packing and one eighth of the tetrahedral holes are
occupied by divalent metal ion (A2+) and one half of the octahedral holes are occupied by trivalent metal ions (B3+). Thus in
a unit cell there are four oxide ions, one divalent metal ion(A2+) and two trivalent metal ions (B3+). The general formula of
the compound is AB2O4.
Examples: MgAl2O4,ZnAl2O4, ZnFe2O4 etc.,
40) The crystal structure present in Al2O3 is called as
1) corundum structure 2) spinel structure 3) rock-salt structure 4) Fluorite structure
Note: In the corundum structure, anions form hexagonal closest packing and cations are present in 2/3 of the octahedral
holes. The general formula of the compound is M2O3.
Examples: Fe2O3, Al2O3, Cr2O3 etc.,
41) Inverse spinel structure is found in
1) Chromite 2) Magnetite 3) Spinel 4) Corundum

X-RAY DIFFRACTION AND BRAGGS EQUATION

1) The diffraction of barium with X - radiation of wavelength 2.29A0 gives a first order diffraction at
300. What is the distance between diffracted planes ?
1) 2.29 A0 2) 2.73 A0 3) 4.58 A0 4) None
Formula : n=2d sin
2) At
what angles for the first order diffraction, spacing between two planes respectively are and
?
2 0
1) 90 & 300 2) 300 & 900 3) 900 & 00 4) 00 & 900
3) An X - ray beam of wavelength 71pm was scattered by a solid. The angle of diffraction (2 ) for
a second order reflection is 140661. The inter planar distance in the crystal will be
1) 710 pm 2) 559 pm 3) 142 pm 4) 71 pm
4) The interplanar distance in a crystal used for X-ray diffraction is 0.2nm. The angle of incidence ( )
of X-rays is 90. If the diffraction is of first order, Find the wavelength of the X-rays.
1) 0.062 nm 2) 0.23nm 3) 0.43nm 4) 0.11nm
5) A first order diffraction of an X-radiation by crystal planes, separated by a distance of 231 pm, in
a solid is observed at a reflection angle of 300. By using same radiation the first order diffraction is
observed at 600 in another solid. The interplanar distance in the second solid will be
1) 462 pm 2) 400 pm 3) 115.5 pm 4) 322 pm
6) A first order diffraction by a crystal plane is observed at an angle of 150. by using x - rays of
wavelength of 258 pm. If the interplanar distance is 500 pm, the second order of diffraction will be
observed at
1) 7.280 2) 10.50 3)31.170 4) 9.20
 DEFECTS IN CRYSTALS
MAGNETIC & ELECTRICAL PROPERTIES
1) The incorrect statement related to schottky defect is
1) It is a stiochiometric point defect
2) Equal number of cations and anions are missing from their lattice points.
3) Shown by strongly ionic crystals with high co-ordination number.
4) Density & covalent nature are increased.
Note: In Schottky defect, pair of holes are formed as both the cations and anions (with equal but opposite charge) leave the
lattice points and move out of the crystal. This is a stoichiometric point defect. The defected crystal is electrically neutral. But
density and covalent nature are decreased. Dielectric constant and hence ionic nature are increased. Defected crystals show
little electrical conductivity. Schottky defects are shown by ionic compounds with high co-ordination numbers. The difference
in the sizes of oppositely charged ions is small. Usually these defects are shown by compounds of big sized alkali and alkaline
earth metals. Eg., NaCl, CsCl etc.,
It is a thermodynamic defect. The number of defects increase with increase in temperature.

2) Creation of holes due to transfer of a cation from its lattice point to the interstitial space is called
1) Schottky defect 2) Metal excess defect 3) Frenkel defect 4) F-centre formation
Note: In Frenkel defect, the cations, being small can move from the lattice points to interstitial spaces and thus by creating
holes. This is a stoichiometric point defect. The defected crystal is electrically neutral. But density and covalent nature are
decreased. Dielectric constant and hence ionic nature are increased. Defected crystals show little electrical conductivity. This
defect is shown by ionic compounds with low co-ordination numbers. The difference in the sizes of oppositely charged ions
must be large. Usually these defects are shown by compounds of small sized transition metals.
Eg., AgCl, AgBr, ZnS etc.,
It is also a thermodynamic defect. The number of defects increase with increase in temperature.

3) Frenkel defect is not possible in

1) AgCl 2) ZnS 3) CsCl 4) AgBr
4) Which of the following is not common for Schottky and Frenkel defects?
1) Stoichiometric 2) Increase in the number of defects with temperature
3) Decrease in density 4) Low lattice energy and stability of defected crystal
5) Consider the following statements.
a) Both Schottky and Frenkel defects are non stiochiometric defects
b) Crystals with Schottky and Frenkel defects show little electrical conductivity
c) Frenkel defect is shown by ionic compounds with high co-ordination numbers and with big sized
cations.
 d) Crystals with Schottky and Frenkel defects are electrically neutral
The correct statements are
1) a & b 2) b & d 3) c & d 4) b, c & d
6) Which of the following point defect causes decrease in density of crystal without disturbing the sto-
ichiometric ratio ?
1) Frenkel defect 2) Schottky defect 3) Metal excess defect 4) All
7) The stoichiometric point defect possible in AgBr is
1) Schottky defect 2) Frenkel defect 3) Both 1 & 2 4) Metal excess defect
8) Consider the following statements related to metal excess defect.
a) Metal excess arises due to extra cation and electrons present at interstitial voids in a crystal
b) Metal excess defect arises when anions leave the crystal from their lattice points .
c) Crystal with metal excess defect is not neutral.
d) Metal excess defect is a non-stiochiometric defect.
The correct statement(s) is/are
1) a & c 2) b, c, & d 3) a, b & d 4) All

9) In which of the following non-stoichiometric defect, the cation occupies the interstitial site
1) Schottky defect 2) Frenkel defect
3) Metal excess defect 4) Metal deficiency defect
10) LiCl shows pink color when heated in Li vapour due to
1) Metal deficiency defect 2) Schottky defect 3) F-Centre formation 4) Frenkel defect
Note : F-Centres are formed when an electron occupies anion vacancty in the crystal. They import color and paramagnetic
nature to the crystals
Eg : KCl in K vapours is blue lilac in color NaCl in Na vapour is yellow is color.
11) ZnO turns yellow upon heating because of
1) Metal excess defect 2) Metal deficiency defect 3) Frenkel defect 4) All
Note : When heated ZnO loses oxide ions reversibly. Excess Zn2+ ion and electrons are accomodated interstitially. Due to
presence of odd electrons, ZnO turns yellow. The electrical conductivity is also improved.
This type of defect due to pressence of extra cation and electtrons is also shown by CdO, Cr2O3 and Fe2O3.
12) The formula of wustite ranges from Fe0.93O to Fe0.96O instead of FeO. It is due to presence of
1) Frenkel defect 2) Schottky defect 3) Metal deficiency defect 4) Metal excess defect
Note : Some compounds cannot be prepared in ideal stiochimetric proportions due to metal dificiency defect. This defect
arises when a metal cation is missing from its lattice points and the cahrge is balanced by an adjacent metal ion with extra
exhibited by compounds of transition metals which can exhibit variable valency. As a result, there compounds show non
stoichiometric formulae. Eg : VOX (x can be 0.6 - 1.3), Fe0.95O
13) Following are the statements relating to defects in crystals
a) Frenkel defect is shown by ionic compounds where there is large difference in size between posi-
tive and negative ions.
b) Zinc oxide turns yellow upon heating due to formation of metal deficiency defect
c) The vacant anion sites occupied by electrons are called F-Centres
d) The number of schottky and Frenkel defects decreases with increase in temperature
The correct statements are
1) a only 2) a & c 3) a, b & c 4) a, c & d
14) Select the incorrect statement.
1) Schottky defect is shown by CsCl
2) Frenkel defect is shown by ZnS
3) F-Centres are formed due to leaving of metal ion from the lattice point.
4) Metal deficiencies defect is formed when the metal can exhibit variable oxidation number.
15) The composition of a sample of wustite is Fe0.93O. What percentage of iron is present as Fe(III)?
1) 7% 2) 15.05% 3) 30% 4) 26.3%
16) Addition of little SrCl2 to NaCl produces
1) Cation vacancies 2) Anion vacancies 3) Both cation & anion vacancies 4) None
Note : When NaCl is doped with SrCl2, Sr2+ ions displace Na+ ions from their lattice points. Also at the same time, equal number
of Na+ ions from other lattice sites move out of the crystal and thus by creating cation vacancies. Thus formed solids are called
substitutional solids other examples:- AgCl doped by CdCl2.

17) If NaCl is doped with 10-4 mole% of SrCl2, the concentration of cation vacancies would be
1) 10-4 mole-1 2) 6.022 x 1017 mole-1 3) 6.002 x 10-4mole-1 4) 6.022 x 10-8 mole-1
18) Which one of the following is the correct statement ?
1) Brass is an interstitial alloy, while steel is a substitutional alloy.
2) Brass is a substitutional alloy, while steel is an interstitial alloy.
3) Brass & steel are both substitutional alloys.
4) Brass & steel are both interstitial alloys.
19) AgCl is crystallised from molten AgCl containing little CdCl2. The solid obtained will have
1) Cationic vacancies equal to number of Cd2+ ions incorporated
2) Cationic vacannies equal to double the number of Cd2+ ions incorporated.
3) Anionic vacancies
4) Neither cationic nor anionic vacancies.
20) The type of electrical conductivity shown by crystals with F - Centres is
1) n-type semiconductivity 2) p-type semiconductivity 3) Super conductivity 4) None
21) The conductivity of semiconductors is in the range of
1) 10-20 ohm-1 cm-1 2) 107 ohm-1 cm-1 3) 10-6 to 104 ohm-1 cm-1 4) None
22) Choose the correct statement
1) The energy gap between conduction band and valence band in metallic conductors is very large.
2) The energy gap between conduction band and valence band in semiconductors is very large.
3) Electrical conductivity of semiconductors increases with increasing temperature.
 4) Electrical conductivity of conductors increases with increasing temperature.
23) Which of the following is an intrinsic semiconductor
1) Si 2) Si doped with As 3) Fe 4) Both 1 & 2
24) Silicon doped with III A group elements exhibit
1) n-type semi conductivity 2) p-type semi conductivity 3) Both 1 & 2 4) None
25) Germanium doped with phosphorus acts as
1) n-type semiconductors 2) p-type semiconductor
3) super conductor 4) Intrinsic conductor.
26) Solar photovoltaic cell used to convert radiant energy into electrical energy consists of
1) a pnp triode 2) a pn diode 3) an npn triode 4) None
27) Which of the following is incorrect statement about super conductivity.
1) Super conductors show zero resistance to electrical conductivity.
2) The electrical resistance becomes zero at absolute zero temperature for all the substance
3) Super conductors are good insulators
4) None
28) Match the following
A) Ferro magnetic 1) MnO, MnO2, FeO, NiO etc.,
B) Dia magnetic 2) Fe3O4, MgFeO4 etc.,
C) Anti ferri magnetic 3) ZnO, TiO2, NaCl etc.,
D) Ferri magnetic 4) Fe, Co, Ni etc.,
The correct matching is
A B C D
1) 4 3 2 1
2) 4 3 1 2
3) 3 4 1 2
4) 4 2 3 1
29) The temperature above which the ferromagnetism is lost is called
1) Transition temperature 2) Bohr temperature 3) Curie temperature 4) none
30) The phenomenon of production of electricity by a polar crystal when mechanical stress is applied to
it is called.
1) Antiferro electricity 2) Piezoelectricity 3) Magnetic electricity 4) None
31) A ferro electric substance is
1) KH2PO4 2) BaTiO3 3) Rochelle salt 4) All
Note : Ferroelectric substances are piezoelectric crystals with permanent dipoles.
32) Piezo-electric crystals with zero net dipole moment are called
1) Ferro electric 2) Pyro electric 3) Antiferro electric 4) None
33) The substance which exhibits anti-ferroelectricity is
1) BaTiO3 2) PbZrO3 3) KH2PO4 4) All
34) The crystals which produce electricity upon heating are referred to as
1) Ferro electric 2) Pyro electric 3) Antiferro electric 4) None
35) The Ferro magnetic substance used in audio and video tapes is
1) FeO 2) CrO2 3) MnO 4) BaTiO3.

REVISION
1. An AB2 type structure is found in :
a) N2O b) NaCl c) Al2O3 d) CaF2
2. If the number of atoms per unit in a crystal is 2, the structure of crystal is :
a) Simple cubic b) body centred cubic ( bcc )
c) octahedral d) face centred cubic ( fcc )
3. The intermetallic compound LiAg crystallizes in cubic lattice in which both lithium and silver have
 co - ordination number of eight. The crystal class is :
a) Simple cubic b) body centred cube
c) face centred cube d) none of these
4. The vacant space in the bcc unit cell is :
a) 23% b) 26% c) 32% d) none of these
5. Potassium fluoride has Nacl type structure. What is the distance between K+ and F- ions if cell
edge is a cm ?
a a
a) cm b) cm c) 2a cm d) 4a cm
2 4
6. Braggs law is given by the equation :
d
a) n 2 sin b) n 2 d sin c) 2 n d sin d) n sin
2 2
7. The interionic distance for cesium chloride crystal will
a 2a 3a
a) a b) c) d)
2 3 2
8. Sodium metal crystallizes as a body centred cubic lattice with the cell edge 4.29A0. what is the
radius of sodit atom ?
a) 1.857 x 10-8 cmb) 2.371 x 10-7 cm c) 3.817 x 10-8 cm d) 9.312 x 10-7 cm
9. The edge of unit cell of fcc crystal of Xe is 620 pm. The radius of Xe atom is :
a) 189.37 pm b) 209.87 pm c) 219.25 pm d) 235.16 pm
10. A metal has bcc structure and the egde length of its unit cell is 3.04 A0. The volume of the unit cell
in cm3 will be :
a) 1.6 x 1021cm3 b) 2.81 x 10-23 cm3 c) 6.02 x 10-23 cm3 d) 6.6 x 10-24 cm3
11. A compound is formed by elements A and B. This crystallizes in the cubic structure when atoms
A are at the corners of the cube and atoms B are at the centre of the body. The simplest formula
of the compound is :
a) AB b) AB2 c) A2B d) AB4
12. In a cubic structure of compound which is made from X ad Y, where X atoms are at the corners of
the cube. The molecular formula of the compound is :
a) X2Y b) XY2 c) XY3 d) X3Y
13. The structure of MgO is similar to NaCl. what would be the co-ordination number of magnesium?
a) 2 b) 4 c) 6 d) 8
14. Most crystals show good cleavage because their atoms, ions or molecules are :
a) weakly bonded together b) strongly bonded together
c) spherically symmetrical d) arranged in planes
15. An example of a non - stoichiometric compound is :
a) PbO b) NiO2 c) Al2O3 d) Fe3O4
16. Doping of silicon ( Si ) with boron ( B ) leads to :
a) n - type semiconductor b) p - type semiconductor
c) metal d) insulator
17. In the laboratory, sodium chloride is made by burning the sodium in the atmosphere of chlorine
which is yellow in colour. The cause of yellow colour is :
a) presence of electrons in the crystal lattice
b) presence of Na+ ions in the crystal lattice
c) presence of Cl- ions in the crystal lattice
d) presence of face centred cubic crystal lattice
18. Frenkel defect is caused due to :
a) the shift of a positive ion from its normal lattice site to an interstitial site.
b) An ion missing from the normal lattice site creating a vacancy
 c) An extra positive ion occupying an interstitial position in the lattice
d) An extra negative ion occupying an interstitial position in the lattic
19. Schottky defect generally appears in :
a) KCl b) NaCl c) CsCl d) all of these
20. Due to Frenkel defect, the density of ionic solids :
a) increases b) decreases c) does not change d) change
21. Na and Mg crystallize in bcc and fcc type crystals respectively, then the number of atoms of Na
and Mg present in the unit cell of their respective crystal is :
a) 2 and 4 b) 4 and 2 c) 9 and 14 d) 14 and 9
22. An ionic compound has a unit cell consisting of A ions at the corners of a cube and B ions on the
centres of the faces of the cube. The empirical formula for this compound
a) AB b) A2B c) A3B d) AB3
10g
23. The number of atoms in 100g of an fcc crystal with density, d and cell edge equal to100
cm 3
pm, is equal to :
a) 1 x 1025 b) 2 x 1025 c) 3 x 1025 d) 4 x 1025
24. Potassium has a bcc structure with nearest neighbour distance 4.52 A0. Its atomic weight is 39. Its
density ( in kg m 3 ) will be :
a) 454 b) 804 c) 852 d) 908
25. In orthorhombic, the value of a , b and c are respectively 4.2 A , 8.6A and 8.3 A0.Given the
0 0

molecular mass of the solute is 155 g mol 1 and that of density is 3.3 g / cc, the number of
formula units per unit cell is
a) 2 b) 3 c) 4 d) 6
26. A solid has a structure in which W atoms are located at the corners of a cubic lattic O atoms
at the cube. The formula for the compound is
a) Na2WO3 b) Na2WO2 c) NaWO2 d) NaWO3
27. In a solid AB having the NaCl structure, A atoms occupy the corners of the cubic unit cell. If
all the centre of the face - centred atoms along one of the axes are removed, then the resultant
stoichiometry of the solid is :
a) AB2 b) A2B c) A3B4 d) A4B3
28. The pyknometric density of sodium chloride crystal is 2.16 x 103 kg m-3, while its X - rays density
is 2.178 x 103 kg m-3. The fraction of unoccupied sites in sodium chloride crystal is :
a) 5.96 b) 5.96 x 101 c) 5.96 x 102 d) 5.96 x 103
29. What type of crystal defect is indicated in the diagram below ?
Na+ Cl- Na+ Cl- Na+ Cl-
Cl- Cl- Na+ Na+
Na+ Cl- Na+ Na+ Cl-
Cl- Na+ Cl- Na+ Cl-
a) Schottky defect b) Frenkel defect
c) Interstitial defect d) Frenkel and Schottky defect
30. Assertion : In any ionic solid ( MX ) with schottky defects, the number of positive and negative
ions are same
Reason : Equal number of cation and anion vacancies are present.
Choose the correct answer.
a) Both assertion and reason are true and the reason the correct explanation of the assertion
b) Both assertion and reason are true but reason is reason the correct explanation of the assertion
c) Assertion is true but reason is false
d) Assertion is false but reason is true
31. Total volume of atoms present in a face - centred cubic cell of a metal is ( r is atomic radius ) :
20 3 24 3 12 3 16 3
a) r b) r c) r d) r
3 3 3 3
 SOLUTIONS & COLLIGATIVE PROPERTIES
IIT-JEE
CONCENTRATION
1) Match the following
A) Gas in solid 1) Soda water
B) Solid in liquid 2) Brine solution
C) Solid in solid 3) Air
D) Gas in liquid 4) H2 occluded in Pd
5) Magnalium
Correct matching
A B C D
1) 4 2 5 3
2) 4 5 2 1
3) 4 2 3 5
4) 4 2 5 1
Hint : Soda water = CO 2 in water
Brine = NaCl in Water
Air = O 2 (and other gases) in N 2
Magnalium = Mg (1-15%) in Al (99-85%)
2) Not a homogeneous mixture
1) Soda water 2) aqueous sugar solution
3) Sodium amalgam 4) Milk
Note : In case of milk, fine liquid fat particles are dispersed in water. It is not a true solution.
3) The molarity of 500 cc of solution containing 0.2 moles of NaCl.
1) 0.2 mole L-1 2) 0.4 mole L-1 3) 0.1 mole L-1 4) 0.8 mole L-1
Hint : Molarity is no. of moles of solute per litre of solution.
4) The molarity of H2SO4 solution is 2 M at 27oC. What will be its molarity at 100oC ?
1) = 2 M 2) < 2 M 3) > 2 M 4) All
Hint : Molarity is altered with volume of the solution.
5) The molarity of 250 ml of solution containing 0.365 g. of HCl.
1) 0.04 M 2) 0. 04 m 3) 0.01 M 4) 0. 02 M
6) What is the molarity of 2% NaOH solution ?
1) 20 M 2) 10 M 3) 0.5 M 4) 0.2 M

% WV X 10
Formula : M
Formula weight

7) The molarity of 5.3% Na2CO3 solution of specific gravity 1.1 is

1) 0.55 M 2) 5.3 M 3) 0.53 M 4) All

% W X 10 X d
W
Formula : M
Formula weight

8) The weight of H2SO4 in 200 mL of 0.2 M H SO4 solution is

2
1) 3.92 grams 2) 39.2 grams 3) 9.8 grams 4) 0.98 grams
9) What is the weight percentage of 1 M Na2 SO4 solution ?
1) 1.42% 2) 14.2% 3) 0.29% 4) 2.9%
Note : Weight percentage is weight of solute in 100 ml of solution.
10) The weight percentage of 4 M H2O2 solution of the specific gravity is 1.36 is
 w w w
1) 20 % w
2) 10 % V
3) 10 % w
4) None
-1
11) The density (in g. mL ) of a 3.60 M sulfuric acid solution that is 29% H2 SO4 by mass will be
1) 1.22 2) 1.45 3) 1.64 4) 1.88 (AIEEE-2007)
12) 4.6 g of ethyl alcohol is dissolved in 1000 g of water. The molality of the solution is
1) 4.6 m 2) 0.1 m 3) 0.46 m 4) 0.01 m
Hint : Molality is no. of moles of solute dissolved in 1 Kg of solvent.
13) Two moles of glucose is dissolved in 500 mL of water. The molality will be
1) 1.8 m 2) 18 m 3) 10 m 4) 4 m
Hint : Density of water is approximately 1 g. mL-1
14) The weight of NaOH in 10 mL of 2 m NaOH solution of specific gravity 1.08 is
1) 0.8g 2) 1.6 g 3) 2 g 4) 1.08 g
w
15) The molality of 20% w NaOH solution is.
1) 20 m 2) 2 m 3) 6.25 m 4) 2.65 m
Hint: weight of solvent = weight of solution - weight of solute
16) What is the molality of 9.8% H2SO4 solution of specific gravity 1.098
1) 1 m 2) 1.098 m 3) 9.8 m 4) 2 m
Hint : First calculate weight of the solution
weight = density X volume
17) 120 g of NaOH is added with one litre of water. The molarity of the solution formed is
1) 3 M 2) > 3 M 3) < 3 M 4) None
Hint : The final volume of the solution is more than one litre
18) The molarity of pure water is
1) 5.55M 2) 55.5M 3) 1M 4) 100M
19) For a given aqueous solution , the relation between molality (m) and molarity (M) is
1) m = M 2) m < M 3) m > M 4) All
20) One mole of a solute, occupying 100mL, is dissolved in 1000 g of a liquid A. The density of
liquid A is 2 g.mL-1 If the solution formed is ideal, then
1) M = m 2) M > m 3) M < m 4) None
21) 20 g of NaOH is present in one litre of solution. Its normality is
1) 0.5 N 2) 1 N 3) 2 N 4) 20 N
W 1
Formula : Normality ( N ) x
G. E.W V (in lit )

22) 4.9 g of H2SO4 is present in 250 mL of solution. The molarity and normality of the solution are ,
respectively.
1) 0.1 M & 0.2N 2) 0.2M & 0.4N 3) 0.2 M & 0.2N 4) 0.1 M & 0.1N
23) The weight of H3PO4 in 500 mL of 0.3N H3PO4 solution is.
1) 0.3 g 2) 9.8 g 3) 0.98 g 4) 4.9 g
Hint : Basicity of H PO = 3
3 4
24) The normality of 5.7% Al2(SO4)3 solution is
1) 5.7 N 2) 2 N 3) 1 N 4) None
FW
Hint: EW of Al 2 (SO 4 ) 3
6

25) The specific gravity of 31.6% w/w KMnO4 solution is 1.5. The normality of the solution in the
acidic medium is
1) 15 2) 1.5 3) 31.6 4) 3.16
 w
% X d X 10
w
Formula : N
G .E .W

7+ 2
Hint : Mn Mn (in acidic medium)

26) The normality of 2.36M H2SO4 solution is

1) 4.72N 2) 1.5 3) 1.18N 4) None
Formula : N = M X basicity (for acids)
27) The molarity of 0.3N Ba(OH)2 solution is
1) 0.6M 2) 0.3M 3) 0.1M 4) 0.15M
Formula : N = M X Acidity (for bases)
28) 5.26 g of KMnO4 is present in 100 cc of a solution. What is its normality in basic medium.
1) 5.26N 2) 1N 3) 3.16N 4) 2N
7+ 4
Hint : Mn Mn (in basic medium)

29) The number of H+ ions in 100 mL of 0.1M H2SO4

1) 6.023 X 1021 2) 1.2046 X 1022 3) 3.10 X 1021 4) All
30) The solution with least molarity is
1) 1N HCl 2) 1N H2SO4 3) 1N Na3PO4 4) None
31) The amount of HNO3 to be added to double the concentration of 500mL of 1M HNO3.
1) 63 gr 2) 6.3 gr 3) 31.5 gr 4) 12.6 gr
32) The ratio of volumes of 2 M and 4M solutions to be mixed to get 500mL of 3M solutions.
1) 1 : 2 2) 1 : 1 3) 2 : 1 4) 2 : 4
33) 500 ml of 0.4M Na3PO4 solution is diluted to 0.1M solution. The volume of solvent
required is.
1) 2000 mL 2) 1500mL 3) 1000mL 4) All
H in t : U se M V M V
1 1 2 2

34) 300 mL of 2M NaOH solution is added to 200 mL of 0.5M NaOH solution.

What is the final molarity?
1) 14M 2) 1.4M 3) 0.7M 4) 7M
M 1V1 M 2V2
Hint: M mix
V1 V2

N N
35) 10 mL of HCl solution is mixed with 125 mL of H 2 SO4 and the resultant solution is
2 5
made up to 1 Litre. The normality of the final solution is
1) 0.03 N 2)0.01 N 3) 0.3 N 4) 0.5 N
36) What are the volumes of 3M HCl and 5M HCl solutions, respectively, to be mixed to get 2
litres of 3.5M HCl solution?
1) 1.5 L & 5 L 2) 2 L & 3 L 3) l L & l L 4) 1.5 L & 0.5 L
-
37) Equal volumes of lM KNO3 and lM Al (NO3)3 solutions are mixed. The concentration of NO3
ions in the final solution is
1) 2M 2) 1M 3) 4M 4) 0.5M
-
Note : 1M Al(NO 3)3 contains 3M NO ions.
3
38) 10 mL of 1M Na2 CO3 solution is made upto 1 litre by adding water. The normality of the final
solution is
1) 0.01 N 2) 0.1 N 3) 0.2 N 4) 0.02 N
 -
39) 20 mL of 1M NaCl is added to 10 mL of 2 M AgNO3 . The concentration of Cl ions in the final
solution is
1) 0.5M 2) 0. 4M 3) 1.5M 4) None
- -
Note : All the Cl ions are precipitated out as AgCl. Hence the final concentration of Cl will be almost zero.
40) Which of the following solutions contains more number of ions?
1) 9M KNO3 2) 8M NaCl 3) 4M Al2 (SO4 )3 4) 6M Na2 SO4
41) A 0.02N NaCl solution is diluted by 100 times. The number of moles of NaCl will be
1) increased 2) decreased 3) unchanged 4) Cannot say
Hint : There is no change in the number of moles of solute during dilution. Only the concentration is changed.
42) Which of the following graph represents the variation of molality (m) with temperature (T)

1) 2)

Molality (m)
Molality (m)

T emperature (T) T emperature (T)

3) 4)
Molality (m)

Molality (m)

T emperature (T) T emper ature (T )

Hint : Molality is independant of temperature

43) The equivalent weight of K2 Cr2 O7 , when it is used as an oxidising agent in acidic medium is
(gram atomic weights of K=39.1, Cr = 52 , O = 16)
1) 98 g 2) 49 g 3) 294 g 4) None

Hint: Cr6+ Cr3+ (in acidic medium)

Formula weight
GEW
6
44) Match the following
Reaction Equivalent weight of the reactant
GMW
A) C2 O4 2- CO2 1)
2
GMW
B) FeSO4 Fe3+ 2)
1
GMW
C) H3 PO4 PO4 3- 3)
3
GMW
D) KMnO4 Mn2+ 4)
5
 Correct matching is
A B C D
1) 1 2 4 3
2) 1 2 3 4
3) 2 1 4 1
4) 4 3 2 1
45) The equivalent weight of H3PO4 in the following reaction is
2 H3 PO4 + Ca(OH)2 Ca (H2 PO4 )2 + 2H2 O
MW MW MW
1) 2) 3) 4) All
1 2 3
Note : Equivalent weight of a substance depends on the reaction.
46) 300 mL of 0.1M BaCl2 is added to 100 mL of 0.1M Na3 PO4 . The amount of Ba3 (PO4 )2
precipitate formed is
1) 10-3 moles 2) 2 x 10-3 moles 3) 5 x 10-3 moles 4) 5 x 10-2 moles
Hint : 3 BaCl2 + 2 Na3PO 4 Ba3 (PO 4 )2 + 6 NaCl
3 moles 2 moles 1 mole
47) Choose the incorrect statement.
1) One equivalent weight of an acid is completely neutralised by one equivalent weight of a
base
2) One mole of an acid is always completely neutralised by one mole of a base.
3) One equivalent weight of an oxidising agent oxidises one equivalent weight of a reducing
agent
4) All are incorrect.
48) The volume of 0.1N KOH required to neutralise completely a 20mL of 0.2N H2SO4 is
1) 10mL 2) 40mL 3) 10mL 4) 20mL
Hint : Use the formula N V =N bV b
a a
49) 25 mL of 0.2 M Na2CO3 is completely neutralised by 12.5 mL of HCl solution. What is the
molarity of HCl solution?
1) 0.8 M 2) 0.4 M 3) 0.2M 4) 0.1M
50) 100mL of 0.2 M KMnO4 oxidises 50mL of oxalic acid solution in acidic medium completely. The
molarity of oxalic acid is
1) 1M 2) 0.2M 3) 0.4M 4) 2M
-2 2+
Hint : KM n O 4 + C 2O 4 Mn + CO 2
oxidant reductant
Formula : N V = N r Vr
o o
N o = M o x no. of e- gained by KMnO 4
N r = M r x no. of e- lost by C 2 O 4 2-
51) 20 mL of H2SO4 is required to completely neutralise 10 mL of 0.2M NaOH solution. The weight
of H2SO4 in 500 mL of H2SO4 solution is
1) 4.9g 2) 2.45g 3) 9.8g 4) None
52) 0.18gr of a metal (Atomic weight = 54g) reacts completely with 100mL of 1M HCl. The valency
of the metal is
1) 1 2) 2 3) 4 4) 3
weight w
Hint : no. of equivalents (n )=
e equivalent weight(EW)
 A to m ic w e ig h t A .W
E .W
v a len c y

53) 'x' g of a metal 'M' is completely reacted with 100 ml of 0.2N HCl. If the atomic weight of metal
is 100x g, then the formula of its sulfate salt is
1) M2 SO4 2) MSO4 3) M2 (SO4 )3 4) M(SO4 )2
54) 20g of a bivalent metal liberates 11.2 litres of H2 gas at STP by reacting with excess of acid
solution . The metal is
1) Mg 2)Al 3) Ca 4) Ba
55) 10mL of 0.2M KMnO4 solution is required to oxidise 20mL of 0.3M KI solution completely.
The change in oxidation state of Mn in this reaction is.
1) Mn7+ Mn2+ 2) Mn7+ Mn3+
3) Mn4+ Mn7+ 4) Mn7+ Mn4+
H.W : Write the balanced equation for the reaction

KMnO4 6 KI 4 H 2 O 2 MnO2 3 I 2 8 KOH

56) 18g of glucose is dissolved in 1800 g of water. The mole fraction of glucose is
1) 0.1 2) 0.01 3) 0.001 4) 1
n glucose
Formula : X =
glucose n glucose+ n water

57) The mole fraction of urea in its aqueous solution is 0.23. The mole fraction of water is
1) 0.46 2) 0.77 3) 0.23 4) 1.8
58) Which method of expression of concentration has no units and independant of temperature?
1) Normality 2) Molality 3) Mole fraction 4) All
w
59) The mass percentage of ethyl alcohol in water is 23% . The mole fraction of alcohol is
w
1) 0.208 2) 0.104 3) 1.04 4) 3.26
Hint : solution contains 23 g ethyl alcohol + 77g water
-1
60) 10 mL of a liquid (density = 4.9 g. mL ) is dissolved in 0.18Kg of water. If the mole fraction of the
liquid is 0.01, then its molecular weight will be
1) 98 g 2) 49 g 3) 4.9 g 4) 490 g
Hint : For very dilute solutions

nsolute
X
solute nsolvent

61) The molality of an aqueous solution of urea is 3 m. What will be its mole fraction?
1) 0.3 2) 0.18 3) 0.054 4) 0.003
Hint : For dilute solutions

molality x MWsolvent
X solute
1000
 VAPOUR PRESSURE

1) The vapour pressure of a liquid does not depend on

1) Nature of liquid 2) Temperature 3) Surface area 4) None
2) The rate of vapourisation of a liquid depends on
1) Temperature 2) Nature of liquid 3) Surface area 4) All
3) The vapour pressure of a liquid at its boiling point is
1) equal to atmospheric pressure 2) Lower than atmospheric pressure
3) Greater than atmospheric pressure 4) None
4) The vapour pressure of pure water at 373 K is.
1) 1 atm 2) 76 atm 3) 100 atm 4) 273 atm
5) The boiling points of liquids A,B & C are 350K , 490K and 630K respectively. The correct
diagram of graphs representing their vapour pressures against different temperatures.
1) 2)
A C B
vapour pressure

vapour pressure
A

T emper ature T emper ature

3) 4)
A B C A B C
vapour pressure

vapour pressure

Temper ature T emper ature

6) Which of the following represents graph of logP against 1/T according to Clausius-clapeyron
equation (where P = vapour pressure and T = temperature)
1) 2)
log P

log P

1/ T 1/T

3) 4)
log P

log P

1/ T 1/ T
 Hint : Clausius - clapeyrons equation is
H va p
ln P C
RT
H.W : What is the slope of the curve in the given graph ?

H vap
Ans :
2 .3 0 3 R
7) Which characterizes the weak inter molecular forces of attraction in a liquid ?
1) High boiling point 2) High vapour pressure
3) High critical temperature 4) High heat of vapourisation
8) At equIlibrium, the kinetic energies of vapour and liquid are
1) Equal 2) Not equal 3) Equal only at boiling point 4) All
9) According to Raoults law, the partial vapour pressure of a liquid in a solution is
1) inversly proportional to its mole fraction 2) directly proportional to its mole fraction
3) equal to its mole fraction 4) greater than the vapour pressure of pure liquid.
10) According to Raoults law, the vapour pressure (P) of an ideal solution containing two miscible
liquids i.e., A and B, is
1) P PAo X A PBo X B 2) P PAo X A PBo X B
3) P PAo X A PBo X B 4) All
11) A solution of two liquids behaves ideally when
1) Hmixture 0 2) Smixture 0 3) Vmixture 0 4) Hmixture 0
12) An ideal solution is
1) Benzene + toluene 2) n-Hexane + n-Heptane
3) Chloroben zene + Bromobenzene 4) All
13) Which, among the following solutions, shows positive deviation from Raoults law
1) Ethanol + Water 2) Ether + Acetone
3) Carbontetrachloride + acetone 4) All
14) The partial vapour pressure of liquid A in a solution showing positive deviation from Raoults law
is given by
1) PA = P0A XA 2) PA > P0A XA
3) PA < P0AXA 4) PA = XA
15) The vapour pressure (P) of a solution showing negative deviation from Raoults law is given by
(solution contains two liquids i.e, A and B)
1) P = P0A XA+ P0BXB 2) P = P0A XA - P0B XB

3) P < P0AXA+ P0B XB 4) P > P0AXA+ P0BXB

16) The solution which shows negative deviation from Raoults law is
1) CH3COOH + C5H5N 2) H2O + HNO3
3) CH3COCH3 + CHCl3 4) All
17) For a solution showing positive deviation from Raoults law
1) H mixing 0 2) Vmixing 0
3) Both 1 & 2 4) None
18) The graph of vapour pressure of solution showing positive deviation from Raoults law is

1) P
total 0
2) 0
P P P
A total A
vapour pressure

vapour pressure
0 0
P P
B B

0 X 1 0 X 1
A A
1 XB 0 1 XB 0

3) 0
4) P
P total 0
A P
A

P
vapour pressure

vapour pressure
P total 0
B P
B

0 X 1 X 1
A 0 A
1 XB 0 XB
1 0

H.W: Which graph shows negative deviation from Raoults law?

Answer: 3
19) The forces of attraction in the following solution are greater than those of in their component pure
liquids
1) Benzene + Toluene 2) Ethanol + Water 3) Acetone + Chloroform 4) Acetone + Ether
20) 50 mL of ethanol is mixed with 50 mL of water. The volume of the solution formed will be
1) = 100 mL 2) > 100 mL 3) < 100 mL 4) None
Hint : Vmix 0 i.e., shows positive deviation from Raoult's law

21) The vapour pressure of water at 300K in a closed container is 0.4 atm. If the volumeof the con-
tainer is doubled its vapour pressure at 300K will be
1) 0.8 atm 2) 0.2 atm 3) 0.4 atm 4) 0.6 atm
22) The vapour pressure of deliquescent substance is
1) Equal to the atmospheric pressure 2) Equal to the pressure of water vapour in air
3) Greater than the pressure of water vapour in air
4) Less than the pressure of water vapour in air
Note : Deliquescent substance absorbs water from air and becomes liquid (by dissolving in water).

COLLIGATIVE PROPERTIES
1) The property which depends only on the number of particles and not on the nature of particles is
1) Relative lowering of vapour pressure 2) Elevation in boiling point
3) Depression in freezing point 4) All
2) Choose the incorrect statement
1) The vapour pressure of a solution containing a non volatile solute is inversely proportional to the
mole fraction of solute.
2) The lowering of vapour pressure of a solution containing a non volatile solute is proportional to
the mole fraction of solute.
3) The vapour pressure of a solution containing a non volatile solute is proportional to the mole
fraction of volatile solvent.
4) None.
3) The vapour pressure of a dilute solution (P) containing a non volatile solute is ( Let P01 = vapour
pressure of pure solvent, X1 & X2 = molefractions of solvent and solute respectively)
1) P = P01 X1 2) P = P01 (1-X2) 3) both 1 & 2 4) None
4) The relative lowering of vapour pressure of a dilute solution containing a non volatile solute is
1) equal to mole fraction of solute 2) equal to mole fraction of solvent
3) equal to mole fraction of solution 4) greater than mole fraction of solvent
5) 6 g of Urea is dissolved in 90g of water. The relative lowering of vapour pressure is equal to
1) 0.01 2) 0.06 3) 1.1 4) 0.02
Hint: Urea (NH 2 CONH 2 ) is a non volatile and non electrolytic substance.

P
Formula : Relative lowering of vapour presure X2
P0

where P = lowering of vapour pressure

0
P = vapour pressure of pure solvent

X 2 = mole fraction of solute

6) Calculate the amount of glucose present in 90g of water when the relative lowering of vapour
pressure is 0.02.
1) 9g 2) 12g 3) 18g 4) 24g
Hint: The molecular formula of Glucose is C 6 H 12 O 6
7) The lowering of vapour pressure of a solution containing 15g of non electrolyte in 90g of water at
373K is 1.013 X 103N.m-2. The molecular weight of the solute is
1) 300g.mole-1 2) 90g.mole-1 3) 150g.mole-1 4) 135g.mole-1
Hint: 1 atm = 1.013 X 10 5 N.m -2
8) 1g of a non volatile and non electrolytic solute is dissolved in 78g of benzene at 780C. The molecu-
lar weight of solute is 100g.mole-1. What will be the vapour pressure of solution at 780C.
1) 75.24 mm Hg 2) 780 mm Hg 3) 684 mm Hg 4) 752.4 mm Hg
Hint: The boiling point of benzene is 78 0 C
9) 10g of a non volatile and non electrolytic solute is dissolved in 1000g of benzene. The vapour
pressure is lowered by 0.5%. What is the molecular weight of solute?
1) 312g.mole-1 2) 156g.mole-1 3) 78g.mole-1 4) 100g.mole-1
P 0.5
Hint :
p0 100

10) The vapour pressure of an a aqueous solution of sucrose is 0.99 atm at 373 K. The molality (m) of
the solution is
1) 0.99m 2) 0.55m 3) 5.5m 4) 37.3m
P molality x MWsolvent
Hint: p0 =X solute
1000
11) The lowering of vapour pressure of 1% (w/w) aqueous solution of a non volatile and non electro-
lytic solute is 1.52 mm of Hg at 373K. The molecular weight of the solute is
1) 91g 2) 180g 3) 30g 4) 909g
12) The vapour pressure of a solvent is decreased by 10mm of Hg by adding a non volatile solute. The
mole fraction of solute is 0.14. What would be the molefraction of solvent if decrease in vapour
pressure is 20 mm of Hg
1) 0.28 2) 0.14 3) 0.72 4) 0.86
13) A 6 % glucose solution and 2 % solution of 'x' show same relative lowering of vapour pressure.
Assuming 'x' to be a non-electrolyte, the molecular weight of 'x' is
1) 30g.mole-1 2) 60g.mole-1 3) 90g.mole-1 4) 180g.mole-1
Hint : Molefractions and hence the number of moles of glucose and x are equal.

14) Correct pair of aqueous solutions with equal vapour pressures.

1) 0.1M urea, 0.2M sucrose 2) 0.1M NaCl, 0.1M glucose
3) 0.1M Na2SO4, 0.1M KCl 4) 0.2M urea, 0.1M NaCl
15) The vapour pressure of aqueous solution of K3[Fe(CN)6] is same as that of 0.4M aqueous
solution of urea. Then the concentration of K3[Fe(CN)6] is
1) 0.4M 2) 0.1M 3) 0.2M 4) 0.8M
3
water
Hint: K 3 Fe CN 6 3 K ( aq ) Fe CN 6
( aq )

16) The lowering of vapour pressure of solution containing 'X' is twice of solution
containing 'Y', then (both 'X' & 'Y' are non electrolytes)
1) The MW of 'X' is twice of 'Y' 2) The MW of 'Y' is twice of 'X'
3) The mole fraction of 'X' is twice of 'Y' 4) The mole fraction of 'Y' is twice of 'X'
17) An aqueous solution of Ca(HCO3)2 is heated strongly and filtered. The vapour pressure of clear
filtrate is
1) Greater than that of pure water 2) less than that of pure water
3) Equal to that of pure water 4) Can not say
2+
Hint : Ca aq 2 HCO3 aq CaCO3 s CO2 g H 2 O( l )

18) The vapour pressure of an aqueous solution containing sucrose at 1000C is

1) = 76 cm Hg 2) > 76 cm Hg 3) < 76 cm Hg 4) = 100 cm Hg
19) Which of the following aqueous solutions has the minimum boiling point ?
1) 0.1M NaCl 2) 0.2M urea 3) 0.1M sucrose 4) 0.05M CaCl2
20) The vapour pressure of an aqueous solution of 0.2m glucose is 1atm at 100.360C. What is the
molal boiling point elevation constant of the solvent ?
1) 1.8 2) 1.8 K.mole-1 3) 1.8 K.Kg.mole-1 4) 1.8 Kg-1.mole-1
Hint : Elevation in boiling point = Tb K b . m

where K b Molal boiling point elevation constant (or) ebbulioscopic constant

m Molality
-1
Note : The unit of K b is Kelvin.Kg.mole

21) 0.2g of a non volatile and non electrolytic solute is dissolved in 20g of a liquid to elevate the boiling
point of the liquid by 0.180C. The ebbulioscopic constant of the liquid is 4.212 K.Kg. mole-1 .
What is the molecular weight of solute ?
1) 23.4g.mole-1 2) 234 g.mole-1 3) 117 g.mole-1 4) 202g. mole-1
w2 1000
Hint : Tb K b . m K b . .
MW2 w 1

Where w 2 = wt. of solute

MW2 = Molecular wt. of solute
W1 = Weight of solvent
22) The vapour pressure of a liquid becomes equal to 1 atm at -730C. The molar heat of vaporisation
and molecular weight of liquid are 40 J.mole-1 and 180g.mole-1 respectively. What is its ebbulioscopic
constant ?
1) 1.496 K.Kg.mole-1 2) 149.6 K.Kg.mole-1 3) 1.8 K.Kg.mole-1 4) 40 K.Kg.mole-1
2

Hint : K b
M
R Tb
0
1

H vap 1000

where R Gas constant

0
Tb Boiling point of pure liquid (solvent)

H vap Molar heat of vapourisation

M1 Molecular weight of liquid (solvent)

23) 0.6 g of urea is dissolved in 1 mole of propyl alcohol. The molal boiling point elevation constant of
propyl alcohol is 0.18 K.Kg.mole-1. Calculate the elevation in boiling point.
1) 0.03 K 2) 1.66 K 3) 3.3 K 4) 0.33 K
24) The aqueous solution showing maximum depression in freezing point is
1) 0. 1M CaCl2 2) 0.3M urea 3) 0.1M Na3PO4 4) All
25) 2g of non electrolytic solute is dissolved in 36g of water. The depression in freezing point observed
is 1.08 K. The cryoscopic constant of water is 1.8 K.Kg. mole-1. What is the molar mass of solute.
1) 9.25g.mole-1 2) 18g.mole-1 3) 92.5g.mole-1 4) 180g.mole-1
w2 1000
Hint : Depression in freezing point = Tf K f . m K f . .
MW2 w1

Where Kf = molal freezing point depression constant (or) cryoscopic constant

w 2 = wt. of solute
MW2 = Molecular wt. of solute
W1 = Weight of solvent
26) The latent heat of fusion of water is 3.35 X 105J.Kg-1. Calculate the depression in freezing point of
1m aqueous solution of glucose.
1) 0.00185 K 2) 1.85 K 3) 0.0185 K 4) None

2 2

Hint : K f
R Tf M
0

1
0
R Tf
Hfusion = lf .M1
Hfusion 1000 lf .1000
2

T f
R Tf
0

.m
lf .1000

where R Gas constant

0
Tf Freezing point of pure liquid (solvent)

H fusion Molar heat of fusion

l f = latent heat of fusion

M1 Molecular weight of liquid (solvent)

m = Molality

27) The freezing point of acetamide in glacial acetic acid is 298K. At this temperature, the crystals of
1) acetamide appear first 2) acetic acid appear first
3) both appear together 4) None
Hint : Always crystals of pure solvent seperate out first at the freezing point of solution.
28) How many grams of glucose should be dissolved in 100g of water in order to produce a solution
with a 1050C difference between the freezing point and the boiling point. (Kf = 1.86K.Kg.mol-1
and Kb = 0.51K.Kg.mole-1).
1) 18.2g 2) 37.9g 3) 180g 4) 72g

Hint : T f Tb

Tf T f0 Tb0 Tb
0

Tf +Tb + Tb0 -Tf0 =105 C
0

or Tf +Tb + 1000C-00C =105 C
Tf +Tb =50 C
But Tf = K f m

and Tb = K b m
0
Kf m + Kbm = 5 C
29) Ethylene glycol is used as an anti freeze in radiators to
1) increase the boiling point of water 2) decrease the freezing point of water
3) decrease the boiling point of water 4) freeze the water above 00C.
30) The depression in freezing point of an aqueous solution is 0.670C. What is its relative lowering of
vapour pressure?(Kf= 1.8 K.Kg.mole-1)
1) 0.0067 2) 0.042 3) 0.21 4) 0.42
31) Choose the correct statement
1) Spontaneous flow of solvent from dilute solution to concentrated solution through a semi
permeable membrance is called osmosis.
2) According to vant Hoff, the solute behaves as a gas and the osmotic pressure of solution is
equal to the pressure exerted by solute if it were a gas at the same temperature and occupying the
same volume as that of solution.
3) Reverse osmosis occurs, when a pressure greater than the osmotic pressure of solution is
applied over it
4) All
32) The osmotic pressure of 0.2 molar solution of urea at 270C is
1) 4.92 atm 2) 1 atm 3) 2.7 atm 4) 8.2 atm
Hint : Osmotic pressure ( ) = CRT

n
where C = = molar concentration
V
-1 1
R = Gas constant (0.0821 L.atm.mole .K )

T = Absolute temperature

33) 20g of a non electrolytic solute is present in 500 mL of solution at 270C. The osmotic pressure of
this solution is 1.8 atm. What is the molecular weight of the solute (in g.mole-1) ?
1) 426. 2 2) 547. 3 3) 671.7 4) 323.2
34) The elevation in boiling point of an aqueous solution of glucose is 0.60C. What is its osmotic
pressure at 300K ? (Kb = 1.2 K.Kg. mole-1 & density of solution = 1.09 g. mL-1)
1) 623.6 N.m-2 2) 1247.1 N.m-2 3) 600 N.m-2 4) None
35) The aqueous solution which is isotonic with 0.1M NaCl is
1) 0.1M Glucose 2) 0.1M CH3COOH 3) 0.1M KCl 4) All
36) Insulin is dissolved in a suitable solvent and the osmotic pressures ( in atm.) of solutions of
various concentrations (C) in g/cc are measured at 270C. The slope of a plot of against C is
calculated to be 5 X 10-3. The approximate molecular weight of insulin is
1) 4.51 X 106 g 2) 4.926 X 106 g 3) 6.32 X 105g 4) 9.12 X 107g
n W 1000
Hint : = RT= X X RT
V M.W V

where C = W in grams
1000 RT
Slope = =
C M.W
V in cc

1000 RT W
note : = . is in y = mx form
MW V

37) The correct order of osmotic pressure of equimolar solutions of BaCl2, NaCl and C6H12O6 is
1) NaCl > C6 H12 O6 > BaCl2 2) BaCl2 > NaCl > C6 H12 O 6
3) C6 H12O6 > NaCl > BaCl2 4) All are equal
38) The osmotic pressure of 0.1M NaCl is greater than that of 0.1M CH3COOH. It is due to
1) NaCl is a weak electrolyte 2) CH3COOH is acid
3) CH3COOH is a weak electrolyte 4) All
39) When mercuric iodide is added to an aqueous solution of KI, the
1) Osmotic pressure is decreased 2) Vapour pressure is increased
3) Freezing point is raised 4) All
 Hint : 2KI + HgI 2 K 2 [HgI 4 ]

Initially 2KI gives four ions +

2K and 2I
-

But K 2 [HgI 4 ] gives only three ions +
2K and [HgI 4 ]
2

40) The vant Hoff factor (i) is given by
Abnormal colligative property Actual number of particles in solution
1) 2)
Normal colligative property Number of particles taken
Normal molecular weight
3) 4) All
Abnormal molecular weight
1
Hint : Value of colligative property
Molecular weight

41) The relation between vant Hoff factor (i) and degree of dissociation ( ) of a weak electrolyte A
which dissociates by giving n number of ions ( A nB ) is
i 1 i 1 i
1) 2) 3) 4) None
n 1 n 1 n
Hint : A nB
initia l 1 mole 0
equilibrium (1 - ) n
Total no.of particles in the solution = (1- ) + n
= 1+n -
= 1+ (n-1)

van't Hoff factor (i)

Total no.of particles in the solution

1 n 1
no.of particles taken
1
i = 1+ (n-1)
i-1= (n-1)
i-1
= n-1

42) The relation between vant Hoff factor (i) and degree of association ( ) of A which associates
as follows nA An .
i 1 i 1 i 1 i 1
1) 2) 3) 4)
n 1 1 n 1 1
1 1
n n

Hint : A An
initial 1 mole 0

at equilibrium (1- )
n
1
Total no.of particles in the solution = (1- ) + = 1+ = 1+ ( -1)
n n n
no.of particles in the solution
van't Hoff factor (i) =
no.of particles taken
1
1+ ( -1)
n

1
1 1
i .e., i = 1+ ( -1) i-1= ( -1)
n n
i-1
= 1
1
n
43) Choose the incorrect statement.
1) Vant Hoff factor (i) for aqueous solution of sucrose is one.
2) Vant Hoff factor (i) for aqueous solution of acetic acid is greater than one
3) Vant Hoff factor (i) for a solution of acetic acid in benzene is less than one
4) None
Hint : Vant Hoff factor i = 1 when there is no dissociation or association
i > 1 when there is dissociation
i < 1 when there is association
Acetic acid dimerizes in benzene (a solvent with low dielectric constant)

44) The degree of dissociation ( ) of a weak electrolyte AX BY is related to vant Hoff factor (i) by
the expression.
i 1 i 1 i 1 x y 1
1) 2) 3) 4)
x y 1 x y 1 x y 1 i 1
45) If vant Hoff factor of Ca(NO3)2 is 2.3, then its percentage of dissociation is
1) 22% 2) 65% 3) 60% 4) 44%
46) The molecular weight of acetic acid dissolved in benzene is calculated as 90g.mole-1 by using
osmotic pressure method. What is the percentage of association of acetic acid.
1) 0.33% 2) 0.66% 3) 90% 4) 66.6%
0
47) 0.01m aqueous solution of K3[Fe (CN)6] freezes at -0.062 C. Its % of dissociation is
(Kf =1.86K.Kg. mole-1)
1) 72% 2) 88% 3) 78% 4) 56%
-1
48) A solution containing 0.8716 mole.L of sucrose is iso-osmotic with a 0.5M NaCl solution. What
is the degree of dissociation of NaCl
1) 0.7432 2) 74.32% 3) 0.8716 4) 0.3716
49) The minimum value of vant Hoff factor if a solute undergoes trimerization in a solution is
1) 0.5 2) 1.33 3) 0.33 4) 3
50) The observed molar mass of KCl obtained by freezing point depression method is related to the
actual molar mass (M) as (the degree of dissociation is x)
1) M (1 + x) 2) M / 2x 3) M (1 + x)-1 4) M (1 - x)-1
0
51) At 25 C, a solution containing 0.2g of poly ethene in 100 mL of toluene shows a rise of 4.8mm at
osmotic equilibrium. The molecular weight of polyethene will be (density of the solution =
0.44g.mL-1)
1) 5.29 X 103g 2) 2.98 X 105g 3) 2.39 X 103g 4) 2.39 X 105g
52) A boy manured a rose plant with highly concentrated solution of urea. On the next day
1) the green colour of the plant will be improved. 2) the plant will grow taller.
3) the plant will bear more number of roses. 4) the plant will die.
 1

CHEMICAL THERMODYNAMICS (PART-I)

IIT-JEE & AIEEE
GATE, JAM & CSIR EXAMS

INTRODUCTION & FIRST LAW OF THERMODYNAMICS

1) Which of the following statement is true about thermodynamics
a) Thermodynamics will help in predicting whether a physical or chemical change is possible under
given conditions.
b) Thermodynamics only deals with the initial and final states of the system and is not helpful in
evolving the mechanism of the process.
c) The rate of a reaction can be evolved from thermodynamics.
d) The mechanism of a reaction can be evolved from thermodynamics.
1) a only 2) a & b 3) a,b & c 4) a & d
2) Choose the incorrect statement
1) Open systems can exchange both energy and matter with its surroundings.
2) Closed systems can only exchange energy and do not exchange matter with its surroundings.
3) Isolated systems can exchange energy and matter with its surroundings.
4) None.
3) Which of the following is not an intensive property?
1) Entropy 2) Density 3) Temperature 4) Pressure
4) Which of the following is an extensive property?
1) Entropy 2) Enthalpy 3) Volume 4) All
H
5) Extensive properties, out of a) boiling point, b) viscosity, c) p , d) emf of a cell and e) molar heat
capacity; are
1) a, b & c 2) b & e 3) c & e 4) None
6) Which of the following is not a state function?
1) Internal energy 2) Enthalpy 3) Work 4) Free energy
7) Which of the following is a state function and not an intensive property?
1) Temperature 2) Volume 3) Pressure 4) None
8) In an adiabatic process,
1) dT = 0 2) dU = 0 3) q 0 4) All
Note: In an adiabatic process, there is no exchange of heat between system and surroundings. Hence dq = 0 and dU = w.
However there is change in temperature and internal energy during this process.
9) In which of the following processes, dT =0?
1) Adiabatic process 2) Isobaric process 3) Isothermal process 4) Isochoric process
10) In an isochoric process,
1) dT = 0 2) dP = 0 3) dV = 0 4) dH = 0
Note: in isochoric (dV=0) and isobaric (dP=0) processes, the pressure-volume work is always zero.
11) In a cyclic process,
1) dU = 0 2) dH = 0 3) dT = 0 4) All
12) If the systems A and B are in thermal equilibrium with system C, then system A is also in thermal
equilibrium with system B. In thermodynamics, this statement is known as
 2
1) 1st law 2) 2nd law 3) 3rd law 4) zeroeth law
13) Thermos flask is an example of
1) Closed system 2) Open system 3) Isolated system 4) All
14) The correct statement about isothermal process is
1) dT = 0 2) dU = 0 3) q = -w 4) All
15) The statement which is not true according to 1st law of thermodynamics is
1) Energy can neither be created nor destroyed although it can be changed from one form to an-
other.
2) The total energy of the universe is constant.
3) The change in the internal energy of a closed system is equal to the sum of heat lost or absorbed by
the system and work either done by the system or done on the system
4) The change in internal energy of a system is zero in all the processes
16) The work done during the free expansion of an ideal gas is equal to
1) Pext 2) dV 3) dU 4) zero
17) Which of the following is true about isothermal free expansion of a gas?
1) dU = 0 2) dT = 0 3) PextdV = 0 4) All
18) The work done during isothermal irreversible change will be given by
Vf Vf
1) -Pext(Vf-Vi) 2) 2.303nRT log 3) nRT log 4) zero
Vi Vi
Note: In the irreversible process, the work is done against constant external pressure which differs largely from the internal
pressure.
19) The work done during an isothermal reversible change will be given by
Vf Vf
1) -Pext(Vf-Vi) 2) 2.303nRT log 3) nRT log 4) zero
Vi Vi
Note: In case of reversible process, the internal pressure is almost equal to the external pressure. This internal pressure is
given by nRT / V.
20) Two litres of an ideal gas at a pressure of 10 atm expands isothermally into vacuum until its total
volume becomes 100 litres.The amount of heat absorbed in the expansion is
1) 2.303 J 2) 100 J 3) 90 J 4) None
Note: As the process is isothermal, q=-w=PdV; And as the expansion is done against zero pressure(Pext=0), the work done as
well as the heat absorbed will be zero.
21) Which of the following statements is true
1) The work done in reversible expansion is less than the work done in irreversible expansion.
2) The work done in reversible expansion is equal to the work done in irreversible expansion.
3) The work done in reversible expansion is greater than the work done in irreversible expansion.
4) All.
Note: But in case of compression, |wrev| < |wirrev|
22) Ten litres of an ideal gas at a pressure of 10 atm expands isothermally against a constant pressure of
1 atm. until its total volume becomes 100 litres.The work done in the expansion is
1) -90 L-atm 2) -10 L-atm 3) -23.03 L-atm 4) -230.3 L-atm
Hint: This is the case of irreversible expansion.
23) Ten litres of an ideal gas at a pressure of 10 atm expands reversibly under isothermal conditions until
its total volume becomes 100 litres.The work done in the expansion is
1) -90 L-atm 2) -10 L-atm 3) -230.3 L-atm 4) -100 L-atm
Note: The work done is maximum in case of reversible expansion. (negative sign only indicates the work is done by the
system)
24) The amount of heat absorbed, when 2.5 L of an ideal gas is compressed isothermally under constant
atmospheric pressure until the volume becomes 0.5 L is
 3
1) 2 J 2) -202.65 J 3) +202.6 J 4) -2 J
Note: 1) During isothermal compression, heat is liberated by the system and hence negative with respect to it.
2) 1 L-atm = 101.325 J
25) 2 moles of an ideal gas at STP is expanded isothermally in infinitisimally small steps until the volume
is doubled. The amount of heat absorbed during this process is
1) 1.37 kJ 2) 8.3 kJ 3) -1.37 kJ 4) None
26) 1 liter of an ideal gas, initially at a pressure of 10 atm, is allowed to expand at constant temperature
to 10 liters by reducing the external pressure to 1 atm in a single step. The work done during this
process is
1) 10 L-atm 2) -100 L-atm 3) -9 L-atm 4) 0 L-atm
27) The area of which of the following graph shows PV work done during reversible expansion of ideal
gas at constant temperature?

28) 25 L of an ideal gas is compressed isothermally under constant atmospheric pressure until the vol-
ume becomes 5 L. The change in internal energy is
1) 20 J 2) -2026.5 J 3) +2026 J 4) 0 J
29) There is a balloon of given volume, V1, containing a gas at temperature, T1. When the balloon is
placed in a colder room at temperature, T2, the balloons temperature starts to drop. What are the
signs of the systems q, w, and E for this process?
1) +q, +w, +E 2) -q, -w, -E 3) -q, -w, +E 4) -q, +w, -E
30) 11.2 L of a hydrogen gas at 273 K temperature and 1 atm of pressure in a sealed rigid container is
heated to double its temperature. The change in internal energy dU will be equal to
1) +w 2) +q 3) -w 4) -q
Note: As the process is isochoric, the change in internal energy is only due to exchange of heat
qv dU =
31) An ideal gas at 10 atm pressure and occupying 0.1 L is expanded to 1.1 L by supplying 101.325 J
of heat against constant atmospheric pressure irreversibly. The change in the temperature of the gas
during this process is
1) 10 K 2) 1.1 K 3) 1K 4) No change
Hint: dU = q+w = 101.325 J + (-101.325 J) = 0
 4
32) A gas is allowed to expand at constant temperature from a volume of 1.0 L to 10.1 L against an
external pressure of 0.50 atm. If the gas absorbs 250 J of heat from the surroundings, what are the
values of q, w, and E respectively?
1) 250 J, -461 J & -211 J 2) -250 J, -461 J & -711 J
3) 250 J, -461 J & -711 J 4) 250 J, -4.55 J & 245 J
33) In a process, 800 J of heat is absorbed by a system and 350 J of work is done by the system. The
change in internal energy for the process is
1) 350 J 2) 450 J 3) -450 J 4) -350 J
34) When is dHsys= dEsys?
1) When qv= qp.
2) In reactions involving only liquids and solids.
3) In reactions running under a vacuum (P=0).
4) All
35) Which of the following reactions could do work of expansion on the surroundings?
1) 2CO(g) + O2(g)
2CO2(g)
2) Fe2O3(s) + 2Al(s)
Al2O3(s) + 2Fe(s)
3) CH4(g) + 2O2(g)
CO2(g) + 2H2O(g)
4) 2N2O(g) 2N2(g) + O2(g)
36) Suppose a gas in a piston is expanded at constant pressure and the temperature goes down. Which
of the following correctly describes the signs for the work, the heat for the system and the energy
change of the system?
1) Work is positive, q is negative, and dU is negative.
2) Work is negative, q is may be positive or negative, and dU is negative.
3) Work is positive, q is may be positive or negative, and dU is negative.
4) Work is positive, q is positive, and dU is negative.
37) In order to have E 0 for a process, which of the following conditions must be obeyed ?
a) q > 0
b) w > 0
c) q + w > 0
d) q > 0 such that |q| > |w| (where |q| and |w| are absolute values)
The correct options are
1) a,b,c & d 2) b &d 3) a & d 4) c & d
38) When 2.0 mol O2(g) is heated at a constant pressure of 4.25 atm, its temperature increases from
260 K to 285 K. Given that the isobaric molar heat capacity of O2 is 29.4 J.K-1 mol-1, the change in
the internal energy during the process will be
1) 1054 J.K-1 mol-1 2) 416 J.K-1 mol-1 3) 1470 J.K-1 mol-1 4) 1887 J.K-1 mol-1

ENTHALPY & HEAT CAPACITY

1) The amount of heat exchanged between system and surroundings under constant pressure is called
1) Entropy 2) Enthalpy 3) Internal energy 4) Free energy
Note: The amount of heat exchanged at constant pressure i.e., q p H U PV
2) Enthalpy(H) of a system can be represented by
1) U + PV 2) U-PV 3) q+w 4) dU + PdV
3) Consider the following statements about enthalpy.
a) It is an intensive property
b) It is a state function.
c) It is an extensive property.
 5
d) It is a path function.
The correct statements are
1) a & d 2) b & c 3) a & c 4) b & d
4) Hydrogen chloride gas readily dissolves in water, releasing 75.3 kJ/mol of heat in the process. If one
mole of HCl at 298 K and 1 atm pressure occupies 24.5 liters, find U for the system when one
mole of HCl dissolves in water under these conditions.
1) +2.48 kJ 2) -75.3 kJ 3) -72.82 kJ 4) +75.3 kJ
Hint: The volume of the liquid is negligible. The process is isothermal and isobaric.
Note: -72.82 kJ > -75.3 kJ; So the change in internal energy(dU) will be greater than the change in enthalpy(dH)i.e., dU > dH.
But if absolute values are taken, 75.3 kJ > 72.3 kJ i.e., the heat liberated will be greater than decrement in internal energy. It
is because, the compression of the gas which increases the internal energy. Also remember, the magnitude of work done on the
system is less than heat liberated during the process.
5) One mole of an ideal gas is dissolved in a solvent by liberating 0.27 kJ of heat. What is the change in
internal energy when one mole of gas is dissolved completely in this solvent at 273 K and 1 atm
pressure.
1) -2 kJ 2) -0.27 kJ 3) +2 kJ 4) +0.53 kJ
Note: Now +2 kJ > 0.27 kJ. Therefore dU > dH. This is true even when the absolute values are taken. Why? In this case the
value of work done on the system during compression is greater than the amount of heat lost.
6) If water vapour is assumed to be a perfect gas, molar enthalpy change for vapourisation of 1 mol of
water at 1bar and 100C is 41kJ mol-1. The internal energy change, when 1 mol of water is vaporised
at 1 bar pressure and 100C will be
1) 37.9 kJ mol1 2) 41 kJ mol1 3) 47.9 kJ mol1 4) 18.3 kJ mol1
Reaction: H2(liquid)
H2(gas)

Formula: U H ng RT
Where n g = no. of moles of gaseous products - no. of moles of gaseous reactants

7) Which of the following is not an intensive property?

1) Molar heat capacity 2) Specific heat capacity 3) Heat capacity 4) All
o
8) The amount of heat required to raise the temperature of 1.00 g of aluminium by 1 C is called its
1) Enthalpy 2) Heat capacity 3) Specific heat 4) Molar heat
-1 -1
9) The molar heat capacity for NaCl is 50.50 J mol K . What is the specific heat?
1) 0.8640 J g-1 K-1 2) 50.5 J g-1 K-1 3) 8.640 J g-1 K-1 4) 4.184 J g-1 K-1
10) The amount of heat necessary to raise the temperature of 60.0 g of aluminium from 15oC to 55oC is.
(Molar heat capacity of Al is 24 J mol1K1)
1) 2.133 J 2) 1.066 J 3) 2.133 kJ 4) 2.4 kJ
Formula: q=n.C m .T
Where n = no. of moles
Cm = molar heat capacity
T = raise or lowering of temperature

11) The heat capacity of methyl alcohol (MW = 32.05 g/mol) is 80.3 J mol-1 K-1. The quantity of heat
that will be evolved when the temperature of 2610 g of methyl alcohol falls from 22oC to 2oC
1) 1.5 x 102 kJ 2) 1.3 x 102 kJ 3) 1.7 x 102 kJ 4) 7 kJ
12) The amount of heat absorbed by one mole of an ideal gas in an isochoric process to raise the
temperature from 1.1oC to 11.1oC is 120 kJ/mol. The Cv and Cp values of the gas in kJ mol-1K-1 will
be
1) 12 kJ & 3.7 kJ 2) 10 kJ & 12 kJ 3) 12 kJ & 20.3 kJ 4) 20.3 kJ & 12 kJ
 6

Use the formulae: Cv

U
T v

qv
T

Cp
H
T p

qp
T
C p C v nR

13) The difference in Cp and Cv values for liquids and solids will be equal to
1) R 2) nR 3) 2R 4) 0
14) Choose the incorrect statement
1) The molar heat capacities of the metallic elements are almost identical. This is the basis of the Law
of Dulong and Petit, which served as an important tool for estimating the atomic weights of some
elements.
2) The intermolecular hydrogen bonding in water and alcohols results in anomalously high heat
capacities for these liquids; the same is true for ice, compared to other solids.
3) The heat capacity values for graphite and diamond are very high as the solids that are more
ordered tend to have larger heat capacities.
4) None.
Note: The molar heat capacities of metals are almost equal to 3R.
15) The molar heat capacity values of noble gases at contant volume are almost equal to
3R 5R 7R
1) 2 2) 3) 4) R
2 2
Note: In case of noble gases (which are mono-atomic) only three translational degrees of freedom are possible and each of

1 3R 5
these contribute R to heat capacity and hence the Cv = . The Cp value will be given by Cv + R = R
2 2 2
16) The theoretical molar heat capacities of diatomic molecules at constant volume and at fairly high
temperatures is almost equal to
3R 7R 5R
1) 2) R 3) 4)
2 2 2
Note: Diatomic molecules have 3 translational degrees of freedom (contribution of 3R/2), 2 rotational degrees of freedom

7R
(contribution of 1R/2 from each) and 1 vibrational degree of freedom ( contribution of R). Hence Cv = (at high temp.)
2

5R
But at low temperatures (eg., room temperature), the vibrational degree of freedom can be neglected and hence Cv =
2
In the same way, for poly-atomic molecules, the contributions are as follows

1 1 1 3
From three translational degrees of freedom -- R R R R
2 2 2 2

1 1 1 3
From three rotational degrees of freedom -- R R R R
2 2 2 2
From 3N-6 vibrational modes -- (3N-6)R (where N = number of atoms in poly-atomic molecule)
17) Calculate the enthalpy change on freezing of 1.0 mol of water at10.0oC to ice at 10.0oC. Given
fusH = 6.03 kJ mol1 at 0C; Cp [H2O(l)] = 75.3 J mol1 K1 ; Cp [H2O(s)] = 36.8 J mol1 K1
1) 7.151 kJ 2) -6.03 kJ 3) 3.63 kJ 4) -7.151 kJ
18) If 1000 calories are added to 20 g of ice at -10oC, the final temperature will be
(Specific heat of ice = 0.48 cal/g-K and Heat of fusion of ice = 80 cal/g.)
1) 380 K 2) 0 K 3) 273 K 4) 283.2 K
Note: As the heat supplied is not sufficient to melt the ice completely, finally there will be a mixture of ice and water at 0oC
 7
19) A coffee-cup calorimeter is calibrated by adding 1840 J of heat to the water in the calorimeter and
measuring a 1.72oC rise in temperature. When some NH4Cl(s) is added to the same water in the
calorimeter, the temperature falls by 1.04oC. The enthalpy change due to the dissolving of NH4Cl(s)
is
1) -1112 J 2) +1250 J 3) +3040 J 4) +1112 J
20) Which of the following statements is true?
1) q = dH at constant P; q = dE at constant T
2) q = dH at constant T; q = dE at constant V
3) q = dH at constant V; q = dE at constant P
4) q = dH at constant P; q = dE at constant V
21) An ice cube at 0oC weighing 9.0 g is dropped into an insulated vessel containing 72 g of water at
50oC. What is the final temperature of water after the ice has melted and a constant temperature has
been reached? The latent heat of fusion of ice is 6.01 kJ/mol and the molar heat capacity of H2O is
75.4 J mol-1K-1.
1) 36oC 2) 40oC 3) 44oC 4) 32oC
o
22) What is U o when one mole of liquid water vaporises at 100 C if the heat of vaporisation vap H o
o -1
of water at 100 C is 40.66 kJ.mol ?
1) 40.66 kJ.mol-1 2) 24.66 kJ.mol-1 3) 36.73 kJ.mol-1 4) -40.66 kJ.mol-1
23) The value of Helium gas is equal to
1) 1.67 cal 2) 1.4 cal 3) 6 cal 4) 10 cal

Cp 5
Note: 1.67 cal
Cv 3
3R
For mono atomic gases Cv 3 cal
2
C p Cv R 5 cal

24) Temperature of one mole of Neon gas is increased by 1oC, hence, increase in internal energy is
1) 5 cal 2) 3 cal 3) 9 cal 4) 2 cal
25) Enthalpy change for a reaction does not depend upon
1) the physical states of reactants and products.
2) use of different reactants for the same product.
3) the nature of intermediate reaction steps.
4) the differences in initial or final temperatures of involved substances.
26) The specific heat of water is 4.18 J g-1 K-1 and that of stainless steel is 0.51 J g-1 K-1. The heat that
must be supplied to a 750.0 g stainless steel vessel containing 800.0 g of water to raise its tempera-
ture from 20.0oC to the boiling point of water
1) 6.98 kJ 2) 29.8 kJ 3) 69.8 kJ 4) 298 kJ
27) The temperature of a substance represents
1) the total heat content of a the particles in a substance
2) the speed of the fastest particles in the substance
3) the speed of the slowest particles in the substance
4) the average kinetic energy of the particles in a system.
28) A bomb calorimeter was calibrated by burning a sample of benzoic acid (C6H5COOH) which has
a known heat of reaction, H = 3227 kJ/mol. When 1.22 g of benzoic acid is burned in the
calorimeter, the temperature is increased by 0.75 C. The heat capacity of the calorimeter and its
contents will be
1) 32 kJ K-1 2) 4.3 kJ K-1 3) 83 kJ K-1 4) 43 kJ K-1
29) The heat of combustion of methyl alcohol, CH3OH, is -715 kJ mol-1. When 2.85 g of CH3OH
 8
was burned in a bomb calorimeter, the temperature of the calorimeter changed from 24.05 C to
29.19 C. The heat capacity of the calorimeter is
1) 12.4 kJ/C 2) 124 kJ/C 3) 12.4 J/C 4) 1.24 kJ/C

THERMOCHEMISTRY
1) Which statement is incorrect about endothermic reactions?
1) the system absorbs energy from its surroundings
2) the enthalpy of products is lower than the enthalpy of the reactants
3) the thermal kinetic energy of the surroundings will decrease
4) the enthalpy change will have a positive value
2) Which of the following is the standard state of carbon at STP?
1) C as CO2 (g) 2) C as graphite (s) 3) C as CH4 (g) 4) C as diamond (s)
3) Which of the following statements is/are true about an exothermic reaction?
I) the energy absorbed in bond breaking is more than the energy released in bond formation
II) the system absorbs energy
III) the potential energy of the reactants is less than the potential energy of the products
IV) the thermal kinetic energy of the surroundings will increase
1) I and III only 2) II and III only 3) II and IV only 4) IV only
4) How much heat is absorbed when 3.00 grams of SiO2 react with excess carbon according to the
reaction below? r H o for the reaction is +624.7 kJ.
SiO2(s) + 3C(s) SiC(s) + 2CO(g)
1) 208 kJ 2) 5.06 kJ 3) 10.4 kJ 4) 31.2 kJ
5) H of which of the following reactions is equal to the standard enthalpy of formation( f H o ) of
NH3?
1) 2NH3(g)
3H2(g) + N2(g)
2) NH3(g)
3/2H2(g) + 1/2N2(g)
3) 3H(g) + N(g)
NH3(g)
4) 3/2H2(g) + 1/2N2(g)
NH3(g)
o
Note: The standard enthalpy of formation, f H , is the amount of heat either liberated or absorbed during the formation
of one mole of a compound from its elements under standard conditions.
o
6) Given: H2(g) + Br2(l) 2 HBr(g) ; r H = 72.8 kJ
Calculate the amount of energy absorbed or released when 15.0 g of HBr (g) is formed.
1) 6.75 kJ released 2) 13.5 kJ released 3) 4.85 kJ absorbed 4) 607 kJ absorbed
7) Which of the following has non zero standard enthalpy of formation at 25oC?
1) Cl2(g) 2)O2(g) 3) Na(g) 4) F2(g)
8) The standard heat of formation of NH3 is
(Given N2(g) + 3H2 (g) 2NH (g) ; r H o = -91 kJ )
3
1) +91 kJ 2) + 45.5 kJ 3) -19 kJ 4) -45.5 kJ
9) The enthalpy change for the reaction of 50 mL of ethylene with 50 mL of H2 at 1.5 atm pressure is
H = -0.31 kJ. The change in internal energy will be
1) 0.66 kJ.mol-1 2) -0.3024 kJ.mol-1 3) +0.3024 kJ.mol-1 4) -0.66 kJ.mol-1
10) In a constant-volume bomb calorimeter an unknown compound reacted with excess oxygen to give
carbon dioxide and water. The temperature of 2 kg of water in the calorimeter rose from 12.72oC
to 20.72oC. The heat capacity of the calorimeter is 2.02 kJ.K-1 and the specific heat of water is
4.184 J/goC. The heat given off by the combustion reaction under these conditions is:
1) 41,600 J 2) -41.6 kJ 3) -83.2 kJ 4) -33.5 kJ
Note: The heat given off indicates the internal energy change, as the reaction is occuring at constant volume, and
 9
not is not equal to the enthalpy change.
11) In a constant - volume bomb calorimeter, 4g of methane is burned in excess of oxygen. The tem-
perature of 0.5 Kg of water in the calorimeter rose from 12oC to22oC The heat capacity of calorim-
-1
eter is 20.1 kJ.K . The enthalpy of combustion of methane under standard conditions will be
1) 223.1 kJ.mol-1 2) 891.6 kJ.mol-1 3) 888 kJ.mol-1 4) 20.92 kJ.mol-1
Note: Enthalpy of combustion is the amount of heat liberated when one mole of substance is completely burned in excess of
oxygen at standard conditions (constant temperature and pressure). In this case the amount of heat liberated is equal to U .
This value should be converted to H by using the formula. H U n g RT
12) B5H9 burns in air according to the following reaction.
2B5H9(g) + 12O2(g) 5B2O3(s) + 9H2O(l)
What is the molar heat of reaction for the combustion of B5H9 if the reaction between 0.1 g of B5H9
and excess oxygen in a bomb calorimeter raises the temperature of the 852 g of water surrounding
the calorimeter by 1.57oC? [At wts: B = 10.81 amu; H = 1.008 amu; O = 16.00 amu; the heat
capacity of water is 4.184 J / goC]
1) 5.60 x 103 J/mol 2) 9.14 x 102 kJ/mol
3) 3.54 x 103 kJ/mol 4) 4.46 x 103 kJ/mol
13) In the reaction,
CH4(g) + 2O2(g) CO2(g) + 2H2O(l) ; r H o = -890.4 kJ
At 1.0 atm and 273 K , how much work is involved per mole of CH4(g) with the volume change that
occurs upon reaction.
1) -4.5 kJ 2) -2.2 kJ 3) 2.2 kJ 4) 4.54 kJ
Note: The work is done on the system and is equal to 4.54 kJ. Here n g =-ve and hence, H E i.e., -890.4 kJ< - 885.8 kJ.
But if the absolute values are considered, the decrease in internal energy is less than heat liberated. This is because Some
amount of decrease in internal energy, due to loss of heat, is compensated by compression work done on the system.
14) When burned in oxygen, 10.0 g of phosphorus generated enough heat to raise the temperature of
2950 g of water from 8.0oC to 28.0oC. The heat of formation of P4O10 from P4(s) and O2(g) is
1) -30.6 kJ mol-1 2) -306 kJ mol-1 3) -3060 kJ mol-1 4)-6120 kJ mol-1
15) Using the following data:
I) N2(g) + 3O2(g) + H2(g) 2HNO3(aq) ; H = -414.8 kJ
II) N2O5(g) + H2O(g) 2HNO3(aq) ; H = 218.4 kJ
III) 2H2O(g) 2H2(g) + O2(g) ; H = 483.6 kJ
What is the H for the reaction: 2N2O5(g)
2N2(g) + 5O2(g)
1) 90.8 kJ 2) -876.4 kJ 3) 782.8 kJ 4)1750 kJ

16.

Which thermochemical equation corresponds to the enthalpy diagram shown above?

1) 2 H2 (g) + O2 (g) 2 H2O (g) + 486.3 kJ
2) 2 H2 (g) + O2 (g) + 486.3 kJ 2 H2O (g)
3) 2 H2 (g) + O2 (g) 2 H2O (g) 486.3 kJ
4) H2 (g) + 1/2 O2 (g) 486.3 kJ H2O (g)
17. The standard heat of combustion (H ) of ethanol is 1372 kJ/mol ethanol. How much heat is
released when a 20.0 g sample burns?
1) 68.6 kJ 2) 29.8 kJ 3) 3.16 x 103 kJ 4) 595 kJ
18. Which is the correct enthalpy level diagram for the following reaction:
CaO(s) + 3C(s) + 462.3 kJ CaC2(s) + CO(g)
 10

19. Given the following thermochemical equation

2 C2H3Br (g) + 5 O2 (g) 4 CO2 (g) + 2 H2O (g) + 2 HBr (g) H = 1150 kJ
What is the change in energy accompanying the production of 1.5 moles of CO2(g)?
1) 1725 kJ 2) 766.7 kJ 3) 431.3 kJ 4) 9.799 kJ
20. When 1.75 g of CaCl2 dissolves in 125 g of water in a coffee-cup calorimeter, the temperature
increases by 2.44C. What is the heat change per mole of CaCl2 dissolved? Assume that all the
heat is absorbed by the water.
1) 11.3 kJ/mol of CaCl2 2) 1.13 kJ/mol of CaCl2
3) 729 kJ/mol of CaCl2 4) 80.9 kJ/mol of CaCl2
21. 5.5 g of sodium hydroxide is dissolved in 175 mL of water. Using a coffee-cup calorimeter, the
temperature change of the water is measured to be +2.10C. The specific heat capacity of water
is 4.184 J/gC. What is the thermochemical equation for this process?
1) NaOH(s) NaOH(aq) 1.54 kJ 2) NaOH(s) 1.54 kJ NaOH(aq)
3) NaOH(s) NaOH(aq) 11.2 kJ 4) NaOH(s) 11.2 kJ NaOH(aq)
22. A mass of 100.0 g of dilute hydrochloric acid is placed in a coffee cup calorimeter. The tempera-
ture of the solution is recorded to be 17.5C. A piece of magnesium ribbon of mass 0.601 g is
placed in the solution and the final temperature is recorded to be 39.6C. Calculate the molar
enthalpy change for this reaction : Mg(s) 2 HCl (aq) MgCl2(aq) H2 (g)
1) + 15.4 kJ/mol of Mg 2) - 263 kJ/mol of Mg
3) - 374 kJ/mol of Mg 4) + 5.56 kJ/mol of Mg
23. Which process is not endothermic?
1) H2O(s) H2O(l) 2) 2H2O(g) 2H2(g) + O2(g)
3) H2O(g) H2O(l) 4) Al2O3 + 2Fe(l) 2Al + Fe2O3
o
24. Calculate the H for the following reaction:
2ClF3(g) + 2NH3(g) N2(g) + 6HF(g) + Cl2(g)
Given this information :
ClF3(g) f Ho -261.0 kJ/mol
HF(g) f Ho -271.1 kJ/mol
NH3(g) f Ho -46.11 kJ/mol
1) -2241 kJ 2) - 1013 kJ 3) -578.2 kJ 4) 578.2 kJ
 11
25. Given the thermochemical equation
2Al(s) + 3/2O2(g) Al2O3(s) ; Ho = -95.6 kJ
determine Ho for the following reaction
2Al2O3(s) 4Al(s) + 3O2(g)
1) -95.6 kJ 2) +95.6 kJ 3) -47.8 kJ 4) +191.2 kJ
26. For the reaction:
NH4NO3(s) N2(g) + 2H2O(g) + 1/2O2(g)
o
H = -1.50 kJ/g NH4NO3 (molecular mass = 80.05 amu). If 0.105 g NH4NO3 decompose in
a bomb calorimeter with a heat capacity of 5.510 J/oC initially at 21.00oC, the final temperature of
the calorimeter and its contents will be numerically (in K):
1) 223 2) 281 3) 323 4) 381
27. Calculate the molar enthalpy of combustion of propylene, C3H6(g), when it reacts with O2(g) to
give CO2(g) and H2O(l). [ f H o (C3H6(g)) = +20.4 kJ/mol, f H o (CO2(g)) = -393.5 kJ/mole,

f H o (H2O(l)) = -285.8 kJ/mole]

1) +699.7 kJ 2) -658.6 kJ 3) -1926.3 kJ 4) -2018 kJ
28. Using the following data:
N2(g) + 3O2(g) + H2(g) 2HNO3(aq) H = -414.8 kJ
N2O5(g) + H2O(g) 2HNO3(aq) H = 218.4 kJ
2H2O(g) 2H2(g) + O2(g) H = 483.6 kJ
Determine H for the reaction:
2N2O5(g) 2N2(g) + 5O2(g)
1)149.6 kJ 2) 90.8 kJ 3) -876.4 kJ 4) 782.8 kJ
29. Calculate the standard molar enthalpy of formation of CO2(g) in the reaction:
C(s) + O2(g) CO2(g)
given the following standard enthalpy changes:
2C(s) + O2(g) 2CO(g) Ho = -221.0 kJ
2CO(g) + O2(g) 2CO2(g) Ho = -566.0 kJ
1) -393.5 kJ 2) +393.5 kJ 3) +787.0 kJ 4) -787.0 kJ
o
30. Calculate the H for the reaction:
S(s) + O2(g) SO2(g)
Given the following data:
S(s) + 3/2O2(g) SO3(g) Ho = -395.2 kJ/mol
2SO2(g) + O2 2SO3(g) Ho = -198.2 kJ/mol
1) 592.2 kJ/mol 2) -197.0 kJ/mol 3) -296.1 kJ/mol 4) -593 kJ/mol
31. Given the following data:
3/2O2(g) + 2B(s) B2O3(s) Ho = -1264 kJ/mol
O3(g) + 2B(s) B2O3(s) Ho = -1406 kJ/mol
The change in enthalpy for the reaction converting oxygen (O2(g)) to ozone (O3(g)) at 298 K and
1 atm will be
3/2O2(g) O3(g)
1) -1406 kJ 2) -1264 kJ 3) -2670 kJ 4) +142 kJ
32. Given the following data
N2(g) + O2(g) 2NO(g) H = 180.8 kJ
1/2N2(g) + O2(g) NO2(g) H = 33.9 kJ
calculate the enthalpy change for the following reaction
NO(g) + 1/2O2(g) NO2(g)
1) 214.7 kJ 2) 146.9 kJ 3) -56.5 kJ 4) 56.5 kJ
 12

33. Calculate the enthalpy change, Ho, for the combustion of benzene, C6H6, given the following
C6H6(l) + 15/2O2(g)
6CO2(g) + 3H2O(l)
f H o values in kJ/mol are as follows:
C6H6(l) = 49.0; CO2(g) = -393.5; H2O(l) = -285.8
1) -3169.4 kJ 2) 3267.4 kJ 3) -728.3 kJ 4) -3267.4 kJ
o
34. Calculate H for the reaction: Na2O(s) + SO3 (g) Na2SO4(s) given the following:
(1) Na(s) + H2O(l)
NaOH(s) + 1/2 H2(g) Ho = 146 kJ
(2) Na2SO4 (s) + H2O(l) 2NaOH(s) + SO3(g) Ho = + 418 kJ
(3) 2Na2O (s) + 2H2(g) 4Na(s) + 2H2O(l) Ho = + 259 kJ
1) + 823 kJ 2) 581 kJ 3) 435 kJ 4) + 531 kJ
35. Given equations (1) and (2), calculate the enthalpy change for equation (3).
(1) Pb(s) + PbO2(s) + 2 SO3(g) 2 PbSO4(s) Ho = -775 kJ
(2) SO3(g) + H2O(l) H2SO4(aq) Ho = -133 kJ
(3) Pb(s) PbO2(s) 2 H2SO4(aq) 2 PbSO4(s) 2 H2O(l)
1) 908 kJ 2) 642 kJ 3) 509 kJ 4) + 642 kJ
36. Given that : S(s) + O2(g) SO2(g) H = 296.8 kJ/mol
2 SO3(g) 2 SO2(g) + O2(g) H = + 197.8 kJ/mol
Determine the enthalpy change of the reaction: 2 S(s) + 3 O2(g) 2 SO3(g)
1) 99 kJ 2) 495 kJ 3) + 495 kJ 4) 791.4 kJ
37. Use the following reactions to calculate H for: 4 HCl (g) + O2(g) 2 Cl2(g) + 2 H2O(g)
H2(g) + Cl2 (g) 2 HCl(g) H = 185.0 kJ
2 H2(g) + O2(g) 2 H2O(g) H = 483.7 kJ
1) +113.7 kJ 2) 298.7 kJ 3) +298.7 kJ 4) 113.7 kJ
38. Given equations (I), (II), and (III), calculate the standard enthalpy of formation of acetylene,
C2H2, as shown in equation (IV).
(I) C (s) + O2 (g) CO2 (g) H = 393.5 kJ
(II) H2 (g) + O2 (g) H2O (l) H = 285.8 kJ
(III) 2 C2H2 (g) + 5 O2 (g) 4 CO2 (g) + 2 H2O (l) H = 2598.8 kJ
(IV) 2 C (s) + H2 (g) C2H2 (g)
1) 253.6 kJ 2) 226.6 kJ 3) 1801 kJ 4) -3278 kJ
39) A volume of 50.0 mL of 0.5 M NaOH was added to 20.0 mL of 0.5 M H2SO4 in a calorimeter
whose heat capacity is 39.0 J/K. The temperature of the resulting solution increased by 3.6 C.
The standard enthalpy of neutralization of H2SO4(aq) with NaOH(aq) will be
1) 13.7 kJ mol-1 2) 53.7 kJ mol-1 3) 5.37 kJ mol-1 4) 23.7 kJ mol-1
40) The standard enthalpy of neutralization of acetic acid with sodium hydroxide will be
1) =53.7 kJ mol-1 2) <53.7 kJ mol-1 3) >53.7 kJ mol-1 4) None
Hint: When weak acids or bases participate in the neutralisation, some amount of heat is required for their complete
dissociation. Hence the amount of heat liberated during neutralisation will be less than 53.7 kJ mol-1.
41) The heat of neutralisation of a strong acid and a strong alkali is 57.0 kJ mol-1. The heat released
when 0.5 mole of HNO3 solution is mixed with 0.2 mole of KOH is
1) 57.0 kJ 2) 11.4 kJ 3) 28.5 kJ 4) 34.9 kJ
42) If the bond dissociation energies of XY, X2 and Y2 are in the ratio of 1:2:0.5 and standard heat of
formation of XY is -100 kJ mol-1, then the bond dissociation energy of Y2 will be
1) 400 kJ mol-1 2) 100 kJ mol-1 3) 200 kJ mol-1 4) 800 kJ mol-1
 CHEMICAL THERMODYNAMICS (PART-II)
IIT-JEE

ENTROPY
1) The Kelvins statement of second law of thermodynamics is
1) The entropy of universe increases in a spontaneous process.
2) It is impossible to take heat from a hotter reservoir and completely convert into work by a
cyclic process with out transferring a part of heat to a cooler reservoir.
3) It is impossible for a cyclic process to transfer heat from a body at lower temperature to one at a
higher temperature with out converting some work to heat.
4) All.
Note: 3rd statement is known as Clausius statement of second law of thermodynamics.
2) Choose the incorrect statement.
1) Entropy is a measure of the degree of spreading and sharing of thermal energy within a system.
2) The total change in entropy of system and surroundings is zero in a reversible process.
3) Change in entropy is inversely proportional to the temperature at which the process occurs.
4) Entropy of a perfectly-ordered solid at 0C is zero.
Note: 1) According to third law of thermodynamics, the entropy of a perfectly ordered crystal is zero at absolute zero
temperature.
2) Absolute entropy value of the system is proportional to temperature. But the change in entropy is inversely
related to temperature.
3) The thermodynamical expression for change in entropy is given by
qrev q w q w
1) 2) irrev 3) 4) irrev
T T T T
4) The unit of molar entropy is
1) J.mol-1 2) J.K-1.mol-1 3) J.K-1 4) J.K.mol-1
5) Which of the following is true.
1) Entropy is an intensive property but a state function.
2) Entropy is an extensive property and not a state function.
3) Molar entropy is an extensive property but not a state function.
4) Entropy is an extensive property and a state function.
6) The enthalpy of vaporisation of a substance is 72 J mol-1 and its boiling point is -73oC. The entropy
of vaporization is
1) 72 J mol-1 K-1 2) 0.36 J mol-1 K-1 3) 0.986 J mol-1 K-1 4) 72 J mol K
7) For a process at 350 K and constant pressure, Ssurr is -315 J K-1. The quantity of heat (in kJ)
absorbed by the system is
1) 72 2) 3.15 3) 99.2 4) 3.5
8) Consider the following statements about entropy.
a) An ideal gas occupying larger volume has higher entropy than when it occupies smaller volume
under given conditions.
b) The gases with higher atomic or molecular weights possess greater entropy values.
c) The change in entropy of an ideal gas in isothermal free expansion is always negative.
d) The molar entropy of a dilute solution is greater than that of concentrated solution.
e) Solids possess very high entropy values than liquids and gases.
The incorrect statments are
1) c & e 2) a,c & d 3) a,b & c 4) b,c & e
9) Which of the following contain higher entropy?
1) 1 mole acetylene 2) 1 mole ethane 3) 1 mole ethylene 4) 1 mole methane
 Hint: Entropy will be higher for those molecules with more number of atoms and bonds.
10) Which of the following produces an increase in entropy of the system ?
1) H2O(l) H2O(s)
2) O2(g) + 2SO2(g) 2SO3(g)
3) 2CH3OH(g) + 3O2(g) 2CO2(g) + 4H2O(l)
4) I2(s) I2(l)
11) Which of the following is the significance of Third law of thermodynamics?
1) The absolute entropy of a substance decreases with increasing temperature.
2) The change in entropy of the universe must be positive for a spontaneous process.
3) The absolute value of entropy can be measured for some very pure substances.
4) The entropy of the universe is constant.
12) For which of the following processes does the entropy of the system decrease?
1) Precipitation of silver chloride from a solution containing silver ions and chloride ions.
2) Dissolving table salt in water.
3) Decomposition of liquid hydrogen peroxide to produce liquid water and oxygen gas..
4) Melting of ice.
13) For which one of the following reactions does the entropy of the system increase?
1) NH3(g) + HCl(g) NH4Cl(s) 2) 2H2(g) + O2(g) 2H2O(g)
+ -
3) NH3(g) + H2O(l) NH4 (aq) + OH (aq) 4) 2H2O2(l) 2H2O(l) + O2(g)
14) Which of the following statements best describes the spontaneity of a reaction at 25oC for
which Ssys is negative and Ssurr is positive?
1) The reaction cannot be spontaneous at 25oC.
2) The reaction will be spontaneous at all temperatures.
3) The reaction will be spontaneous only if Ssys is greater in magnitude than Ssurr.
4) The reaction will be spontaneous only if Ssurr is greater in magnitude than Ssys.
Note: For a spontaneous process, S universe S sys S surr 0
15) Which of the following processes will result in a decrease in the entropy of the closed system?
1) Zn2+ (aq) + 4 NH3 (aq) Zn(NH3)42+ (aq)
2) Cl2 (g) (298 K) Cl2 (g) (450 K)
3) ZnS (s) Zn2+ (aq) + S2- (aq)
4) NH3 (g) (3 atm, 298 K) NH3 (g) (1 atm, 298 K)
16) For a certain process S(system) > 0 and S(surroundings) > 0. The process:
1) is spontaneous. 2) is exothermic. 3) is endothermic. 4) is at equilibrium.
17) Arrange the following compounds in order of increasing standard molar entropy at 25oC.
1) ZnS(s) < H2O(l) < C3H8(g) < C2H4(g)
2) ZnS(s) < C3H8(g) < C2H4(g) < H2O(g)
3) C3H8(g) < C2H4(g) < H2O(l) < ZnS(s)
4) ZnS(s) < H2O(l) < C2H4(g) < C3H8(g)
18) The significance of the Second Law of Thermodynamics is that for spontaneous processes the:
1) entropy of the universe is increasing.
2) entropy is the driving force of all chemical reactions.
3) entropy of an ideal solid does not change.
4) absolute value for entropy can be calculated.
19) A change of state occurs within a system and produces 64.0 kJ of heat. This heat is transferred to the
surroundings at a constant pressure and a constant temperature of 300 K. For this process, S of
the surroundings is :
1) 64.0 J/K 2) -213 J/K 3) 213 J/K 4) 0.00 J/K
20) The normal freezing point of water is 0oC. Predict the signs of Ssys, Ssurr and Suniv when H2O
is supercooled and freezes at -10oC and 1atm.
 1) Ssys < 0; Ssurr < 0; Suniv < 0
2) Ssys > 0; Ssurr < 0; Suniv = 0
3) Ssys = 0; Ssurr < 0; Suniv > 0
4) Ssys < 0; Ssurr > 0; Suniv > 0
21) The volume of an ideal gas is doubled in an isothermal process. The change in entropy during this
process is
1) -5.76 J K-1mol-1 2) +5.76 J K-1mol-1 3) +8.3 J K-1mol-1 4) 0 J K-1mol-1
Vf
Formula: For isothermal processes, S 2.303 x nR log
Vi
22) The pressure of 2 moles of a gas is changed from 1 atm to 10 atm at 355.5 K. The change in the
entropy of gas during this process is
1) -38.29 J K-1mol-1 2) +38.29 J K-1 3) -38.29 J K-1 4) +38.29 J K-1mol-1
Pi
Formula: For isothermal processes, S 2.303 x nR log
Pf
23) The absolute entropy of a substance under given conditions cannot be always calculated accurately
T
dT
by using the formula ST C . This is because
0 T
1) The value of C is dependent on temperature and is not a constant.
2) The value of C under constant pressure is always not equal to that under constant volume.
3) The temperature range may encompass the phase change and the entropy change during this
process must be taken into account.
4) All.
24) For mercury the molar entropy of vaporization is 92.92 J K-1 mol-1 and the molar enthalpy of vapor-
ization is 58.51 kJ mol-1. Therefore, the normal boiling point of mercury in oC is:
1) 273oC 2) 357oC 3) 516oC 4) 670oC
vap H
Formula: S
Tb
25) The enthalpy of vaporization of ethanol is 38.7 kJ/mol at its boiling point of 78oC. The change in
entropy of the surroundings when one mole of ethanol is vaporized at 78oC and one atm of pressure
will be
1) +110 J K-1mol-1 2) +220 J K-1mol-1 3) -110 J K-1mol-1 4) 0 J K-1mol-1
26) The significance of the Second Law of Thermodynamics is that for spontaneous processes the:
1) entropy of the universe is increasing.
2) entropy of the surroundings must decrease.
3) entropy of an ideal solid does not change.
4) absolute value for entropy can be calculated.
27) For HI the molar entropy of vaporization is 89.0 J/K mol and the molar enthalpy of vaporization is
21.16 kJ/mol. Therefore, the normal boiling point of HI is:
1) -273oC 2) -35.4oC 3) 23.8 K 4) 42oC
28) A change of state occurs within a system and produces 64.0 kJ of heat. This heat is transferred to the
surroundings at a constant pressure and a constant temperature of 300 K. For this process, S of
the surroundings is :
1) 64.0 J/K 2) -213 J/K 3) -64.0 J/K 4) 213 J/K
29) Which of the following statements is false?
1) Entropy is a measure of the driving force behind chemical reactions.
2) Entropy is a measure of disorder or randomness.
 3) Entropy can be created and destroyed.
4) Entropy is a measure of the number of ways energy can be distributed among the motions of
particles.
Note: Strictly speaking, entropy is a measure of spreading and sharing of thermal energy among the microstates possible in
a system under given conditions.
30) Boiling point of Bromine is 59.20C. The standard molar enthalpy of it is
1) 28 kJ mol-1 2) 38 kJ mol-1 3) -28 kJ mol-1 4) -38 kJ mol-1
Note: According to Troutons rule, the standard molar entropy of vaporisation values of a wide range of liquids are almost
same (85 J K-1mol-1)
o
o
vap H -1 -1
vap S 85 J K mol
Tb
31) The efficiency of engine that is working between a lower temperature 27oC and a higher temperature
327oC is
1) 0.2 2) 0.35 3) 0.5 4) 1
TH TL
Formula: Efficiency of engine =
TH
32) The heat efficiency of an engine will be 100% when the operating lower temperature is
1) 0oC 2) 273 K 3) 0 K 4) 273oC
33) For which one of the following reactions does the entropy of the system decrease?
1) NH4NO3 (s) NH4+ (aq) + NO3- (aq)
2) Ba(OH)2.8H2O (s) + 2 NH4SCN (s) Ba(SCN)2 (aq) + 2 NH3 (aq) + 10 H2O (l)
3) NO (g) + NO2 (g) N2O3 (g)
4) CO2 (s) CO2 (g)
34) Precipitation of the Group I ions in the qualitative analysis scheme as AgCl, Hg2Cl2 andPbCl2 is
spontaneous because
1) Entropy of the system decreases. 2) Entropy of the surroundings decreases
3) Entropy of the universe increases 4) Entropy of the system increases.
35) The standard entropy values (in JK-1 mol-1) of H2(g) = 130.6 Cl2 (g) = 223.0 and HCl (g) = 186.7 at
298 K and 1 atm pressure, then the entropy change for the reaction will be (in JK-1 mol-1)
H2(g) + Cl2 (g) 2HCl(g) is :
1) + 540.3 2) +727.3 3) -166.9 4) +19.8
36) If 900 J/g heat is exchanged at boiling point of water then increase in entropy
1) 43.4 J/mol 2) 87.2 J/mol 3) 900 J/mol 4) zero
37) Oxygen and Helium gases are mixed in ratio of 1 : 1 by weight in a container, then in this process :
1) internal energy decreases 2) internal energy increases
3) entropy increases 4) entropy decreases

GIBBS FREE ENERGY

1) The term T Stotal at constant temperature and pressure is known as
1) Gibbs function 2) Helmholtz function 3) Entropy function 4) All
Note: Gibbs function or Gibbs free energy, G , is equal to T S total at constant temperature and pressure. This is equal to the
maximum useful work other than PV work.
Where as Helmholtz function or Helmholtz free energy, A , is equal to T S total at constant temperature and volume.
This quantiy is equal to maximum work, wmax.
2) Choose the correct equation.
1) T Stotal H system T S system 2) G H system T S system
3) Both 1 and 2 4) None
3) Which of the following is incorrect for a reaction A B?
1) The reaction can spontaneously proceed to the right when G 0 .
2) The reaction can spontaneously proceed to the right when G 0
3) The reaction is at equilibrium when G 0 .
4) All
4) The units of Gibbs function can be given by
1) J K 2) J K-1 3) J 4) J K mol-1
5) Which of the following statement is false?
1) Gibbs free energy is a state function and an extensive property.
2) In G H system T S system , the term T S system represents heat that is wasted in the form PV
work and is not available to do useful work
3) G which is equal to T Stotal represents minimum useful work.
4) Gibbs free energy is not conserved.
Note:1) Molar Gibbs free energy is intensive.
2) Although Gibbs free energy has the units of energy, it cannot be conserved - which is one of the most important
attributes of energy.

1
6) The reaction H 2 ( g ) O2 ( g ) H 2O (l ) is used in fuel cells to produce an electric current.
2
Given the thermodynamic data:
Molar entropies in J mol-1 K-1 for O2(g) =205; for H2(g)=130.6; for H2O(l) =70
and f H o of H2O(l) = 285.9 kJ mol1.
What is the amount of electrical work the same reaction can perform in the fuel cell when carried out
reversibly at 298 K.
1) -237.2 kJ mol-1 2) +285.9 kJ mol-1 3) +237.2 kJ mol-1 1) +2.859 kJ mol-1
Note: The amount of electrical work done by this reaction is equal to the Gibbs free energy change(-237.2kJ mol-1 ). As it is
negative, the reaction is spontaneous. This is the maximum useful work.
During this process some amount of heat is liberated and is given by
o o
T S f H G = 285.9 kJ mol-1 - (-237.2 kJ mol-1 ) = 48.7 kJ mol-1
This is the amount of heat liberated during the compression work done on the system as1.5 moles of gas during the reaction
are disappeared. This is equal to PV work and is not useful.
7) For a particular chemical reaction, Ho is positive and So is negative. Which of the following
statements about the spontaneity of the reaction under standard conditions is TRUE?
1) The reaction will be spontaneous only if the magnitude of Ho is large enough to overcome the
unfavorable entropy change.
2) The reaction will be spontaneous only if the magnitude of So is large enough to overcome the
unfavorable enthalpy change.
3) The reaction will be spontaneous regardless of the magnitudes of Ho and So.
4) The reaction cannot be spontaneous at all temperatures.
8) Which of the following is TRUE for an operating voltaic cell? (Where Ecell = emf of the cell)
1) G > 0 ; Ecell = 0 2) G < 0 ; Ecell < 0
3) G < 0 ; Ecell > 0 4) G = 0 ; Ecell = 0
9) An exothermic reaction which is spontaneous at all temperatures is
1) C(graphite) + O2(g) CO2(g) ; H = 393 kJ
2) 3H2 (g) + N2(g) 2NH3(g) ; H= 46.2 kJ
3) N2O4(g)
2NO2(g) ; H = + 55.3 kJ
 4) All
10) For a particular chemical reaction, both Ho and So are negative. Which of the following state-
ments about the spontaneity of the reaction under standard conditions is true?
1) The reaction will be spontaneous at any temperature.
2) The reaction will be spontaneous only at higher temperatures
3) The reaction will be spontaneous regardless of the magnitudes of Ho and So.
4) The reaction will be spontaneous only if the magnitude of Ho is large enough to overcome the
unfavorable entropy change.
11) Which of the following reactions is unfavorable at low temperatures but becomes favorable as the
temperature increases?
1) 2 CO(g) + O2(g) CO2(g); Ho = -566 kJ; So = -173 J/K
2) 2 H2O(g) 2 H2(g) + O2(g); Ho = 484 kJ; So = 90.0 J/K
3) 2 N2O(g) 2 N2(g) + O2(g); Ho = -164 kJ; So = 149 J/K
4) PbCl2(s) Pb2+(aq) + O2(g); Ho = 23.4 kJ; So = -12.5 J/K
12) For a particular chemical reaction, the values for H and S are both positive. Which of the
following statements is TRUE about this reaction?
1) The reaction is spontaneous at any temperature.
2) The reaction is not spontaneous at any temperature.
3) The reaction is spontaneous when the temperature is high enough to overcome H.
4) The reaction is spontaneous when the temperature is low enough to overcome H.
13) A spontaneous reaction always occurs when:
1) Ho < 0 and So < 0 2) Ho > 0 and So < 0
3) Ho < 0 and So > 0 4) Ho > 0 and So > 0
14) In which case does the spontaneity of a reaction depend on the temperature?
1) H = 0 and S < 0 2) H > 0 and S > 0
3) H < 0 and S = 0 4) H > 0 and S = 0
15) Which of the following statements is True?
1) A process in which the entropy of the system increases will always be spontaneous.
2) An endothermic process can never be spontaneous.
3) An exothermic process that is accompanied by an increase in the entropy of the system will always
be spontaneous.
4) A process in which the entropy of the surroundings increases will always be spontaneous.
16) For a particular chemical reaction at 25oC, H = -536 kJ. Which of the following statements is
TRUE?
1) The reaction will be spontaneous, at any temperature, if S is positive.
2) The reaction will be spontaneous, at any temperature, if S is negative.
3) The reaction will be spontaneous only if G is positive.
4) The reaction can never be spontaneous, at any temperature.
17) All of the gas-phase reactions listed below are endothermic. Which one of these reactions is
most likely to be non-spontaneous at all temperatures?
1) COCl2(g) CO(g) + Cl2(g)
2) 4NO(g) + 6H2O(g) 4NH3(g) + 5O2(g)
3) 2SO3(g) 2SO2(g) + O2(g)
4) N2O4(g) 2NO2(g)
18) For a particular chemical reaction, Ho = +70 kJ and So = +210 J/K. The temperature at which
this reaction would become spontaneous is
1) below 60.3 oC 2) above 333.3 oC 3) above 60.3 oC 4) below 333.3 oC
 Note: For reactions with identical signs of H and S there is a unique temperature at which when G = 0 and T S H .
This is the temperature at which G changes its sign. This is also the temperature at which the system reaches equilibrium.

19) A change in which of the following will also change the value of G for a chemical reaction?
1) partial pressures of either gaseous reactants or products
2) temperature
3) concentration of either reactants or products in aqueous solution
4) All
20) For a particular process at 450 K, G = -5.2 kJ and H = -43.7 kJ. If the process is carried out
reversibly, the amount of useful work that can be performed is
1) -48.9 kJ 2) -5.2 kJ 3) -43.7 kJ 4) -38.5 kJ
21) The following thermite reaction is initiated by burning of a magnesium ribbon.
Fe2O3(s) + 2 Al(s) 2 Fe(l) + Al2O3(s)
For this reaction, the standard enthalpy change is equal to -851.5 kJ and the standard entropy
change is equal to -38.58 J/K. This reaction cannot occur at low temperatures because
1) Enthalpy is favorable and entropy is unfavorable.
2) Neither enthalpy nor entropy are favorable.
3) Both enthalpy and entropy are favorable at high temperatures only.
4) The activation energy is very high.
22. Chemical thermodynamics predicts that materials made of wood, metal, paper, plastic, leather and
rubber react with oxygen in the atmosphere and decompose at 25oC and 1 atm pressure. Which of
the following is responsible for the fact that these reactions are very slow under these conditions?
1) low entropy 2) high enthalpy 3) high activation energy 4) low activation energy
23) Which of the following statements is true?
1) Endothermic reactions are never spontaneous, at any temperature.
2) Exothermic reactions are always spontaneous, at any temperature.
3) Exothermic reactions in which the entropy change for the system is negative are spontaneous at
any temperature.
4) None of the above statements is true.
24) A mixture of hydrogen and chlorine gas remains unreacted until exposed to UV light.Then the follow-
ing reaction occurs very rapidly:
H2(g) + Cl2(g) 2 HCl(g) ; G= -45.54kJ, H= -44.12kJ, S = -4.76 J/K
Select the statements below which best explains this behaviour.
1) The reactants are thermodynamically less stable than the products.
2) The reaction is thermodynamically spontaneous, but the reactants are kinetically stable.
3) The ultraviolet light raises the temperature of the system and makes the reaction spontaneous.
4) The negative value for S slows down the reaction.
25) If a reaction is spontaneous at 27oC and has a standard enthalpy change equal to +150 kJ/mol,
which of the following must be true about the standard entropy of reaction?
1) Standard entropy change < 0 J/mol K
2) Standard entropy change = 27 J/mol K
3) Standard entropy change > 500 J/mol K
4) Standard entropy change = 150 J/mol K
26) The normal freezing point of water is 0oC. Predict the signs of H, S and G when H2O is
supercooled and freezes at -10oC and one atmosphere.
1) H < 0, S < 0, G < 0
2) H < 0, S > 0, G = 0
3) H > 0, S = 0, G > 0
4) H > 0, S > 0, G = 0
27) S > 0 for a certain chemical reaction carried out at constant temperature and pressure . Which of
 the following will be true about spontaneity of the reaction?
1) The reaction is spontaneous if it is endothermic and the temperature is sufficiently high.
2) The reaction is spontaneous, if it is exothermic, at any temperature.
3) The reaction is not spontaneous if it is exothermic and the temperature is sufficiently low.
4) Both 1 and 2.
28) Chloroform, CH3Cl, is a common organic solvent. Consider the following process at 70oC, in a
closed system:
CH3Cl(l) -> CH3Cl (g)
This process is endothermic. Which of the following statements is most likely true regarding the
spontaneity of this process at 70oC?
1) The process will be spontaneous because Ssys is negative.
2) The process will be spontaneous because Ssurr is positive.
3) The process will be spontaneous if the boiling point of CH3Cl is less than 70oC.
4) The process will be spontaneous if the boiling point of CH3Cl is greater than 70oC.
29) Which of the following thermodynamic properties cannot be experimentally determined?
1) So 2) Go 3) Go 4) So
30) An ideal solution is formed spontaneously by mixing equal volumes of benzene and touene. For this
process Hsoln is almost zero. Which of the following will be responsible for the spontaneity of this
process?
1) positive Ssoln 2) negative Ssoln 3) positive Vsoln 4) positive Gsoln
31). Consider the gas-phase reaction of hydrogen, H2, and chlorine, Cl2, to produce hydrogen chloride,
H2(g) + Cl2(g) 2HCl(g)
and the following thermodynamic data :
substance fGo, kJ/mol
H2(g) 0
Cl2(g) 0
HCl(g) -95.30
The value of H (in kJ) for this reaction at 25oC if the standard state entropy change is equal to
o

20.0 J/K.
1) 184.6 kJ 2) 101.26 kJ 3) 196.56 kJ 4) 51.3 kJ
o
o
Note: H of the given reaction is to be calculated and not f H .
32) At elevated temperatures, hydrogen iodide, HI, decomposes to produce hydrogen, H2, and iodine,
I2, as shown in the equation below:
2 HI (g) H2 (g) + I2 (g)
Using the thermodynamic data below, calculate the standard free energy change (in kJ) for this
reaction.
Compound fHo, kJ mol-1 So, J mol-1 K-1
HI(g) 25.9 206.3
H2(g) 0 131.0
I2(g) 62.4 260.6
1) 62.4 kJ 2) 16.9 kJ 3) 32.8 kJ 4) 8.45 kJ
33) Consider the following gas-phase reaction and average bond enthalpies,
2NOCl(g) 2NO(g) + Cl2(g)
bond average bond enthalpy, kJ mol-1
N-Cl 201
N=O 716
Cl-Cl 243
Which of the following statements about the spontaneity of this reaction is true at 25oC?
 1) The reaction will be spontaneous only if the magnitude of H is large enough to overcome the
unfavorable entropy change.
2) The reaction will be spontaneous only if the magnitude of S is large enough to overcome the
unfavorable enthalpy change.
3) The reaction will be spontaneous if both H and S are negative.
4) The reaction cannot be spontaneous at any temperature.
34) Solid ammonium nitrate, NH4NO3 (s), dissolves spontaneously in water at 25oC,
NH4Cl (s) NH4+ (aq) + Cl- (aq)
If this process is endothermic, which of the following is most likely true ?
1) G > 0 2) G = 0 3) S < 0 4) S > 0
o
35) The normal freezing point of NH3 is -78 C at one atmosphere. Predict the signs of H, S, and
G for NH3 when NH3 supercools and then freezes at -80oC and one atmosphere.
1) H < 0, S < 0, G = 0 2) H < 0, S > 0, G < 0
3) H < 0, S < 0, G < 0 4) H > 0, S > 0, G = 0
36) Consider the following gas-phase reaction
H2(g) + CO(g) <==> H2CO(g)
and the following thermodynamic data,
substance Hfo, kJ mol-1 So, J mol-1 K-1
H2(g) 0 131
CO(g) -110 198
H2CO(g) -116 219
Which of the following best explains why this reaction is not spontaneous under standard conditions?
1) Both Ho and So oppose spontaneity..
2) Both Ho and So favor spontaneity..
3) Ho favors spontaneity but So opposes spontaneity..
4) Ho opposes spontaneity but So favors spontaneity..
37) Adsorption of gases on solid surfaces is generally exothermic because:
1) Entropy of the gas and solid increases.
2) Entropy of the gas and solid decreases.
3) Free energy increases.
4) The total entropy of the system and surroundings decreases.
38) The correct relation between change in free energy in a reaction and the corresponding equilibrium
constant Kc is given by:
1) G RT ln K c 2) G RT ln K c 3) G o RT ln K c 4) G o RT ln K c
39) When a reaction is at equilibrium, which of the following statements is true?
1) G = Go 2) G = 0 3) ln Keq = 0 4) Go = 0
40) For the boiling of methanol,
CH3OH(l) CH3OH(g) ; Ho = +38.0 kJ and So = +113.0 J/K.
The temperature at which the value of G becomes equal to zero for this process will be
1) Greater than its boiling point
2) Less than its boiling point.
3) Equal to its boiling point.
4) Can not be calculated unless the G value is given.
41) The following reaction is spontaneous as written:
Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)
Which of the following statements is true?
1) Keq > 1 and Go = 0 2) Keq > 1 and Go < 0
3) Keq < 1 and Go < 0 4) Keq > 1 and Go > 0
42) The equilibrium constant for a chemical reaction will be equal to one when
1) Ho < 0 and So = 0 2) Ho = 0 and So = 0
3) Ho < 0 and So > 0 4) Ho > 0 and So < 0
43) The standard free energy change for the following reaction if the complex ion formation equilibrium
constant, Kf , is equal to 2.1 x 1013.

Cu2+ (aq) + 4 NH3 (aq)
Cu(NH3)42+ (aq)
1) -150 kJ 2) -76 kJ 3) -6.4 kJ 4) 19 kJ
44) Consider the following gas-phase reaction,
2 H2 (g) + O2 (g) 2 H2O (g)
and the corresponding thermodynamic data:
substance Gfo, kJ/mol
H2(g) 0
O2(g) 0
H2O(g) -228.6
The value of the equilibrium constant for this reaction under standard conditions will be
1) 1.4 x 1040 2) 1.4 x 1020 3) 1.4 x 1080 4) 1.4 x 1010
45) Which of the following statements concerning the change in Go and G during a chemical reac-
tion is most correct?
1) Go remains constant while G changes and becomes equal to Go at equilibrium.
2) Both Go and G remain constant during a chemical reaction.
3) Go remains constant if the reaction is carried out under standard conditions; G remains
constant if the reaction is carried out under non-standard conditions.
4) Go remains constant while G changes and becomes equal to zero at equilibrium.
46). Calculate the value of Ka for hydrofluoric acid (HF) at 25oC if the standard free energy change for
the following reaction is equal to +17.9 kJ/mol:
HF (g) + H2O (l)
H3O+ (aq) + F- (aq)
1) 4.0 x 10-38 2) 7.4 x 10-4 3) 9.2 x 10-1 4) 1.4 x 103
47) Hydrogen peroxide decomposes according to the following reaction:
H2O2(l) H2O(l) + 1/2 O2(g)
For this reaction H = -98.2 kJ and S = 70.1 J/K. The approximate value of Kp for this reaction
at 25oC is
1) -1 x 1013 2) -3 x 102 3) 5 x 10-2 4) 7 x 1020